CA1089461A - Stabilisers for synthetic polymers and a process for their preparation - Google Patents
Stabilisers for synthetic polymers and a process for their preparationInfo
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- CA1089461A CA1089461A CA291,095A CA291095A CA1089461A CA 1089461 A CA1089461 A CA 1089461A CA 291095 A CA291095 A CA 291095A CA 1089461 A CA1089461 A CA 1089461A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
ABSTRACT
New piperidine derivatives of 1,3,5-triazine which are useful for improving the resistance of synthetic polymers to light, heat and oxidation.
The new compounds are comprises in the general formula (I) where :
R1, R2, which may be equal or different, each represent one atom of hydrogen, a linear or branched alkyl containing 1 to 18 C, a cyclo-alkyl containing 5 to 18 C, an unsubstituted or substituted aryl containing 6 to 18 C, an arylalkyl containing 7 to 18 C, or a pipe-ridinearadical of formula (II):
(II) in which R3, R4, R6, R7, which may be equal or different, each re-present an alkyl containing 1 to 6 C, and R5 represents H, O, an alkyl of 1 to 12 C, an alkenyl or alkinyl of 2 to 12 C;
X, Y, which may be equal or different, each represent -O-, -S-, -N-R8-, where R8 is H or a linear or branched alkyl containing :
to 18 C, a cycloalkyl containing 5 to 18 C, a substituted or unsubstituted aryl, containing 6 to 18 C, an arylalkyl contain-ing 5 to 18 C, or a piperidine radical of formula (II);
the radicals R1-X-, R2-Y- may also represent radicals of nitroge-nated heterocyclic compounds of 5 to 8 terms joined to the triazino ring by an arom of nitrogen of said radical;
n is a whole number between 7 and 2000;
Z represents a n-valent radical obtained by eliminating n atoms of active hydrogen fromelinear or branched polyamines containing at least 7 primary and/or secondary amino groups, for example the po lyamines characterized by repetitive units of type ;
(III) or (IV) or (V) or (VI) or (VI) in which R9, R10, R11, which may be equal or different, each repre-sent an alkylene of 2 to 12 C, a cycloalkylene of 5 to 12 C, an aryl lene of 6 to 12 C, an arylalkylene of 7 to 12 C, or a radical, R12 is hydrogen, a linear or branched alkyl of 1 to 12 C, a cycloalkyl of S to 12 C, a substituted or unsubstituted aryl of 6 to 12 C, an arylalkyl of 7 to 12 C, and m is zero or l;
in formula (1) the condition that the radicals R1-X or R2-Y-contain at least one piperidine radical of formula (II) must be satisfied.
New piperidine derivatives of 1,3,5-triazine which are useful for improving the resistance of synthetic polymers to light, heat and oxidation.
The new compounds are comprises in the general formula (I) where :
R1, R2, which may be equal or different, each represent one atom of hydrogen, a linear or branched alkyl containing 1 to 18 C, a cyclo-alkyl containing 5 to 18 C, an unsubstituted or substituted aryl containing 6 to 18 C, an arylalkyl containing 7 to 18 C, or a pipe-ridinearadical of formula (II):
(II) in which R3, R4, R6, R7, which may be equal or different, each re-present an alkyl containing 1 to 6 C, and R5 represents H, O, an alkyl of 1 to 12 C, an alkenyl or alkinyl of 2 to 12 C;
X, Y, which may be equal or different, each represent -O-, -S-, -N-R8-, where R8 is H or a linear or branched alkyl containing :
to 18 C, a cycloalkyl containing 5 to 18 C, a substituted or unsubstituted aryl, containing 6 to 18 C, an arylalkyl contain-ing 5 to 18 C, or a piperidine radical of formula (II);
the radicals R1-X-, R2-Y- may also represent radicals of nitroge-nated heterocyclic compounds of 5 to 8 terms joined to the triazino ring by an arom of nitrogen of said radical;
n is a whole number between 7 and 2000;
Z represents a n-valent radical obtained by eliminating n atoms of active hydrogen fromelinear or branched polyamines containing at least 7 primary and/or secondary amino groups, for example the po lyamines characterized by repetitive units of type ;
(III) or (IV) or (V) or (VI) or (VI) in which R9, R10, R11, which may be equal or different, each repre-sent an alkylene of 2 to 12 C, a cycloalkylene of 5 to 12 C, an aryl lene of 6 to 12 C, an arylalkylene of 7 to 12 C, or a radical, R12 is hydrogen, a linear or branched alkyl of 1 to 12 C, a cycloalkyl of S to 12 C, a substituted or unsubstituted aryl of 6 to 12 C, an arylalkyl of 7 to 12 C, and m is zero or l;
in formula (1) the condition that the radicals R1-X or R2-Y-contain at least one piperidine radical of formula (II) must be satisfied.
Description
~ 3~ ~
This invention relates to new piperidine derivatives of 1,3,5-triazine which may be used for improving the resis-tance of synthetic polymers to light, heat and oxidation.
Synthetic polymers generally undergo severe deteri-oration when subjected to the action of sunlight or any other source of ultraviolet light.
To improve the light resistance of said polymers, various stabilizers have been proposed, some of which are widely used industrially such as certain benzophenones, benzo~
10 triazoles, aromatic salicylates, -cyano-acrylic esters, `; `~
organostannic compounds and the like, which although having a certain effectiveness have not enabled the problem to be completely solved.
Various piperidine derivatives with light stabilizing properties for synthetic polymers are also known, but in gene-ral these are compounds of limited compatibility with the polymers and are easily extracted by aqueous solutions of ~;
surface active agents.
These characteristics make such products useless where the stabilized polymers are used for the preparation of fibres or stretched tapes. In such cases, because of the high specific surface of the finished products and the prolonged `~
contact with aqueous solutions of surface active agents during processing, the stabilizers are partly lost and the ~uantity -`~
remaining in the finished fibre is no longer sufficient to give satisfactory light resistance.
Again, commonly used light stabilizers such as ben~
zophenone derivatives have limited light stabilizing e~ficiency for polyolefins when used for thin products such as fibres, 30 stretched tapes and thin films. ~ ~
s ~J~
For such applications there is therefore a require-ment for stabilizers which are more effective in their protec-tion against the damaging action of ultraviolet light and which are also more compatible ancl more resistant to extrac-tion by aqueous solutions of surface active agents.
One object of the present invention is a new class of piperidine derivatives of 1,3,5-triazine which may be used as light stabilizers for synthetic polymers, and which are of high compatibility with polyolefins and possess i~proved re-sistance to extraction when in contact with aqueous solutionsof surface active agents.
A further object of the present invention is the preparation of polymer compositions stabilized against photo-degradation and thermo-oxidation. The triazine compounds of the present invention have the following general formula~
_ ~ `r ~z N ~ ~N
l (I) R2 n where:
Rl, R2, which may be the same or different, each represent one atom of hydrogen, a linear or branched alkyl containing 1 to 18 C, a cycloalkyl containing 5 to 18 C, an unsubstituted or substituted aryl containing a total of 6 to 18 C, an aryl alkyl containing a total of 7 to 18 C, or a piperidine radical ~
of formula (II): ~`
This invention relates to new piperidine derivatives of 1,3,5-triazine which may be used for improving the resis-tance of synthetic polymers to light, heat and oxidation.
Synthetic polymers generally undergo severe deteri-oration when subjected to the action of sunlight or any other source of ultraviolet light.
To improve the light resistance of said polymers, various stabilizers have been proposed, some of which are widely used industrially such as certain benzophenones, benzo~
10 triazoles, aromatic salicylates, -cyano-acrylic esters, `; `~
organostannic compounds and the like, which although having a certain effectiveness have not enabled the problem to be completely solved.
Various piperidine derivatives with light stabilizing properties for synthetic polymers are also known, but in gene-ral these are compounds of limited compatibility with the polymers and are easily extracted by aqueous solutions of ~;
surface active agents.
These characteristics make such products useless where the stabilized polymers are used for the preparation of fibres or stretched tapes. In such cases, because of the high specific surface of the finished products and the prolonged `~
contact with aqueous solutions of surface active agents during processing, the stabilizers are partly lost and the ~uantity -`~
remaining in the finished fibre is no longer sufficient to give satisfactory light resistance.
Again, commonly used light stabilizers such as ben~
zophenone derivatives have limited light stabilizing e~ficiency for polyolefins when used for thin products such as fibres, 30 stretched tapes and thin films. ~ ~
s ~J~
For such applications there is therefore a require-ment for stabilizers which are more effective in their protec-tion against the damaging action of ultraviolet light and which are also more compatible ancl more resistant to extrac-tion by aqueous solutions of surface active agents.
One object of the present invention is a new class of piperidine derivatives of 1,3,5-triazine which may be used as light stabilizers for synthetic polymers, and which are of high compatibility with polyolefins and possess i~proved re-sistance to extraction when in contact with aqueous solutionsof surface active agents.
A further object of the present invention is the preparation of polymer compositions stabilized against photo-degradation and thermo-oxidation. The triazine compounds of the present invention have the following general formula~
_ ~ `r ~z N ~ ~N
l (I) R2 n where:
Rl, R2, which may be the same or different, each represent one atom of hydrogen, a linear or branched alkyl containing 1 to 18 C, a cycloalkyl containing 5 to 18 C, an unsubstituted or substituted aryl containing a total of 6 to 18 C, an aryl alkyl containing a total of 7 to 18 C, or a piperidine radical ~
of formula (II): ~`
-2-~ ~, :. . .
9~
R3 4 :
-~ - R5 (II) R6 7 :
in which R3, R4, R6 ~ R7, which are the same or equal, each represent an alkyl containing 1 to 6 C and R5 represents H, O, an alkyl of 1-12 C, an alkenyl or alkinyl of 2-12C; X, Y, which are the same or different, each represent -O-, -S-, -N- ~ R8 being H or a linear or branchPd alkyl containing 1 to 18 C, a cycloalkyl containing 5-18 C, an aryl containing ~;
6-18 C, an aryl alkyl containing 7-18 C, or a piperidine radi-cal of formula (II~.
The radicals Rl-X-, R2-Y- may also represent radicals 10 of nitrogenated heterocyclic compounds of 5-8 terms joined to ~ -the triazine ring by one atom of nitrogen of said radical, and n is a whole number between 7 and 2000.
Z represents an n-valent radical obtained by elimi-nating n active hydrogen atoms from linear or branched poly- ~ :
amines containing at least 7 primary and/or secondary amino ~
groups, for example polyamines containing repetitive units of ~ I
the type;
-N-Rg- (III) :~
H
or -N-Rg-N-Rlo~ (IV) : ~:
H H ;~
20 or -N-Rg-N-Rlo~ (V) H ,Rll or -CH2-~H- (VI) ~ ~
(CH2)m ~ ~`
NH R12 :~
--3-- ::
in which Rg, R1o, Rll which may be the same or diEferent, each represent a 2-12 C alkylene, a 5-12 C cycloalkylene, a 6-12 C
arylene,a 7-12 C arylalkylene or a -CH2-CH-CH2- radical.
OH
R12 is hydrogen, a 1-12 C linear or branched alkyl, a 5-12 C cycloalkyl, a substituted or unsubstituted 6-12 C
aryl, or a 7-12 C aryl alkyl, and m is zero or 1.
In formula (I), there must be at least one piperi-dine radical of formula (II) present in the Rl-X- or R2-Y-radicals.
Examples of Rl, R2, besides H, are methyl, ethyl, isopropyl, n-butyl, isobutyl, n~hexyl, n-octyl, n-dodecyl, n-octadecyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, phenyl, o-, m-, p-toluyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, ~ -`
a or ~-naphthyl, benzyl, p-methylbenzyl, 2,2,6,6-tetramethyl- -4-piperidyl, 1,2,2,6,6-pentamethyl-4-piperidyl, l-allyl-2,2,6,6-tetramethyl-4-piperidyl.
Examples of R3, R4, R6, R7 are methyl, ethyl, n-propyl, n-butyl, n-hexyl.
Examples of R5, besides hydro~en, are methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-dodecyl, allyl, and propinyl. ~-Examples of X and Y are -O-, -S-, -N-, where R8 besides hydrogen may be methyl, ethyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, n-octadecyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, phenyl, p-toluyl, benzyl, 2,2,6,6- - ~
tetramethyl-4-piperidyl, 1,2,2,6,6-pentamethyl-4-piperidyl, ~ ;
, l-ethyl-2,2,6,6-tetramethyl-4-piperidyl, or 1-n-propyl-2,2,6,6-tetramethyl-4-piperidyl.
The radicals Rl-X-, R2-Y- may also represent radi-cals of 5 to 8 term nitrogenated heterocyclic compounds such as l-pyrrolidinyl, l-piperidinyl, 4-morpholinyl, 4-methyl-1-piperazinyl, 4-methyl-1-homopiperazinyl. `~ ~ ;
:` ' .
-4- `~
1 f R R R are ethylene, 1,2-propylene, trimethylene, hexamethylene, 2,2,4-trimethylhexamethylene, ~ 2,4,4-trimethylhexamethylene, decamethylene, 1,4-cyclohexylene, tr 4,4'-methylene-dicyclohexylene, o-, m-, p-phenylene, o-, m-, p-xilylene, and 2-hydroxy-1,3-propyle~le.
Examples of polyamines containing repetitive units of types (III), (IV), (V) are those polyethyleneimines ob-tained by cationic polymerization of ethyleneimine (Kir~-Othermer Encycl. of Chem. Tech. vol. 17, 406), or those poly-10 amines obtained for example by reacting a primary diamine with a dihaloalkane (see for example Belgium Patent 614,619 and Japanese Patent 10,534/60) or a dihalocycloalkane, or a dihalo-arene, or a dihaloalkarene, or with epichlorohydrine (see for example British Patent 950,852). Examples of polyamines con-taining repetitive units of type (VI) are polyvinylamine (see for example British Patent 772,345) and polymerR and copolymers of allylamine (see for example U. S. A. Patent 3,057,833).
Preparation ~ ;
The triazine compounds of formula (I) may be prepa~
red by reacting a 4,6 disubstitute~ 2-halo-1,3,5-triazine of formula (VII):
N (VII) Rl~ X ~ ~ - halogen N
R2 ;
in which the halogen is preferably chlorine, with polyamines `~
characterized by a repetitive unit of the type: ~`
-N-Rg- (III) ` -~
H
or -N-Rg-N-Rlo~ (IV) H H
or -N-R -N-R - (V) H ,R11 -5- ; `
~IV~
or -C~2-CH- (VI) (CH2)m In the reaction between the reactants of formula (VII) and the polyamines it is preferable to use 1 mole of intermediate (VII) for each NH or NH2 group. However, it is possible to use a smaller quantity of reactant (VII), for example 0.1 to 1 mole for each NH or NH2 group of polyamines, but it is also possible to use an excess of reactant (VII).
The reactions between the halotriazines (VII) and `~
polyamines are conducted preferably in the presence of inert solvents such as acetone, dioxane, toluene, or xylene, working generally at the solvent boiling point.
The reactions are carried out in the presence of organic and inorganic bases for fixing the liberated halogen acid. Triethylamine, tributylamine, sodium hydrate, carbo-nate or bicarbonate, or potassium hydrate or carbonate may ~ `~
for example be used.
In order to better illustrate the present invention,some examples of preparation of the compounds according to the invention are given hereinafter, these examples being given only as non-limiting illustrations. ~;
A) Preparation of 2-chloro-4,6-bis-lN(2,2,6,6-tetramethyl-4-piperidyl)-butylamino~-1,3,5-triazine.
212 g (1 mole) of 2,2,6,6-tetramethyl-4-n-butylamino- ~`
piperidine dissolved in 100 ml of acetone are added to a mix-ture of 92.25 g (0.5 moles) of cyanuric chloride, 700 ml of ~ `
acetone and 600 g of ice. The temperature of the mixture is ~-raised to 35C, then 40 g (1 mole) of sodium hydrate dissolved ~ ' ~;'' ~ ~ -... . .
., ~ in 400 ml of water are added.
; The mixture is agitated for 6 hours at 35-40C. The pre-cipitate obtained is filtered, washed with water and dried over anhydrous CaC12. After crystallization from xylol, a white crystalline powder is obtained having a melting point of 83-85C.
Chlorine = 6,48% (calculated for C29H54ClN7 - 6.62%).
B) Preparation of the poly -(2.4-bis[N(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl¦- derivative of polyethylenimine of molecular weight 450-750.
198 g (0.37 moles) of 2-chloro-4,6-bis-[N(2,2,6,6-tetramethyl-4-piperidyl)-n-butylaminoJ-i,3,5-triazine, 21.5 g of polyethyl-eneimine of molecular weight 450-750, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are heated under reflux `
for 16 hours, under agitation. After filtration, followed by evaporation of the solvent at 120C under reduced pressure (13 mm.Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 120-135C, -N - 20.58%, Cl - 0.17%. The IR spectrum for the product indicates the disappearance of ~.
the primary and secondary amino groups present in the initial polyamine.
Preparation of the poly (2,4-bis[N(2,2,6,6~
tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl)-derivative of polymethyleneimine of molecular weight 1050-1350.
198 g (0.37 moles) of 2-chloro-4,6-bis-[N(2,2,6,6-tetramethyl-4-pipexidyl)-n-butylamino]-1,3,5-triazine, 21.5 g . :: . . .
of polyethyleneimine of molecular weight 1050-135Q, 14.8 g ;~ ~
. -.~ ~. ,, .:
(0.37 moles) of sodium hydrate and 500 ml of xilene are heated `
': ` ' '`' ~'' ~' -7- - ; ~
under reflux for 16 hours, under agitation. After filtering and then evaporating the solvent at 120C under reduced pres-sure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 131-143C, N = 20.71%, Cl =
0.12%. The IR spectrum for the product indicates the disap-pearance of the primary and secondary amino groups present in the intitial polyamine.
EXAMPLE 3 -~
Preparatio~ of the poly (2,4-bis[N-(2,2,6,6-tetra-mèthyl-4-piperidyl)-n-butylamino3-1,3,5-triazin-6-yl- deriva-tive of polyethyleneimine of molecular weight 1650-1950.
198 g (0.37 moles) of 2-chloro-4,6-bis-[N-~2,2,6,6-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 1650-1950, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are heated under reflux for 16 hours, under agitation.
After filtering and then evaporating the solvent at 120C under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 161-175C, N = 20.38~, Cl = 0.23%. The IR spectrum for the product indicates the disappearance of the primary and secon-dary amino groups present in the initial polyamine.
EXAMPLE 4 `
A) Preparation of 2-chloro-4,6-bis[N(2,2,6,6-tetramethyl-4-piperidyl)ethylamino]-1,3,5-triazine.
184 g (1 mole) of 2,2,6,6-tetramethyl-4-ethylamino- '~
piperidine dissolved in 100 ml of acetone are added to a ~ ~;
mixture of 92.25 g (0.5 moles) of cyanuric chloride, 500 ml ~ `~
of acetone and 160 g of ice.
The mixture temperature is raised to 35C, and then :,, 40 g (1 mole) of sodium hydrate dissolved in 100 ml of water are added.
The mixture is agitated for 6 hours at 35-40C, the precipitate is filtered, washed with water and dried over anhydrous CaC12. On crystal~ization from acetone, a white crystalline powder is obtained which melts at 127-129C.
Chlorine - 7.36~ (calculated for C25H46ClN7 = 7.40%).
B) Preparation of the poly (2,4-bis[N(2,2,6,6-tetramethyl-4-piperidyl)ethylamino]-1,3,5-triazin-6-yl) deri-vative of polyethyleneimine of molecular weight 450-750.
177.4 g (0.37 moles) of 2-chloro-4,6-bis[N-(2,2,6,6-tetramethyl-4-piperidyl)-ethylamino]-1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 450-750, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are refluxed for 16 hours under agitation. After filtering and then evapora-ting the solvent at 120C under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtai-ned. M.P. = 168-179C; N = 23.07%; Cl = 0.15%. The IR
spectrum for the product`indicated the disappearance of the `~
primary and secondary amino groups present in the initial polyamine.
Preparation of the poly (~,4-bis[N(2,2,6,6-tetra-methyl-4-piperidyl)ethylamino]-1,3,5-triazin-6 yl) derivative of polyethyleneimine of molecular weight 1050-1350. ~`
177.4 g (0.37 mole) of 2-chloro-4,6-bis[N-(2,2,6,6- `
tetramethyl-4-piperidyl)-ethylamino]-1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 1050-1350, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are re-fluxed for 16 hours under agitation. After filtering and _ g _ -.
then evaporating the solvent at 120C under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 156-167C; N = 22.95~; Cl =
0.10%. The I.R. spectrum for the product indicates the dis-appearance of the primary and secondary amino groups present in the initial polyamine.
~ EXAMPLE 6 f A) Preparation of 2-chloro-4,6-bis(2,2,6,6-tetramethyl-4-piperidyl-amino)-1,3,5-triazine, according to ; 10 the French Patent 2.181.059. 18.45 g (0.1 moles) of cyanuric chloride are suspended in 600 ml of water and then 31.2 g ~`
(0.2 moles) of 4-amlno-2,2,6,6-tetramethylpiperidine and a ~;
solution of 8 g (0.2 moles) of sodium hydrate in 20 ml of water are added. The mixture is agitated for 30 minutes at ambient temperature and is then heated to 90C for 16 hours.
After cooling, the precipitate is separated by fil-tration, washed and dried under vacuum. A white powder is obtained with a melting point of 277-278C.
B) Preparation of the poly [2,4-bis(2,2,6,6-tetramethyl 4-piperidyl-amino)-1,3,5-triazin-6-yl] derivative of polyethyleneimine of molecular weight 450-750. i~
139.7 g (0.33 moles) of 2-chloro-4,6-bis(2,2,6,6- `~
tetramethyl-4-piperidylamino)-1,3,5-triazine, 19.3 g of poly-methy~eneimine of molecular weight 450-750, 13.2 g (0~33 - moles) of sodium hydrate and 800 ml of xylene are refluxed for 16 hours under agitation. -After filtering and then evaporating the solvent ~
at 120C under reduced pressure (15 mm Hg), a fragile resi- ~;
nous substance of light yellow colour is obtained. M.P~
172~195C; N = 25.88%; Cl = 0.25%. The IR spectrum for ~ `
-10- ~,.,~, ';`~
the product indicates the disappearance of the primary and secondary amino groups present in the initial polyamine.
A) Preparation of hexamethylenediamine-epichloro-hydrin copolymer. 580 g (5 moles) of hexamethylenediamine, 370 g (4 moles) of epichlorohydrin and 2000 ml of isopropanol are refluxed for 10 hours. During the last 8 hours 160 g (4 moles) of sodium hydrate are added in small quantities. After filtering and then evaporating the solvent at 120C under vacuum (12 mm Bg), a soft waxy substance of light yellow colour is obtained of molecular weight 800. Total N% = 17.19;
primary N% = 3.27; secondary N~ = 13.78.
B) Preparation of the poly ~2,4-bis[N-2,2,6,Ç-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl)) derivative of the hexamethylenediamine-epichlorohydrin copoly-mer of molecular weight 800.
198 g (0.37 moles) of 2-chloro-4,6-bis[N(2,2,6,6-tetramethyl-4-piperidyl)-butylamino]-1,3,5-tria2ine, 29.6 g of hexamethylenediamine-epichlorohydrin copolymer prepared as ~ ~
under A , 14.8 g (0.37 moles) of sodium hydrate and 500 ml of - ;
xylene are refluxed or 16 hours under agitation.
After filtering and then evaporating the solvent at 120C under reduced pressure (12 mm Hg), a fragile resi-nous substance of light yellow colour is obtained. M.P. =
115-130C; N = 19.12~; Cl = 0.21%. The IR spectrum for the product indicated the disapp~arance of the primary and secondary amino groups present in the initial polyamine. ~;
Compounds of formula (I) are very effective in improving the light, heat and oxidation resistance of syn- -;
thetic polymers such as high and low density polyethylene, --1 1-- .
polypropylene, ethylene-propylene copolymers, ethylene-vinylacetate copolymers, polybutadiene, polyisoprene, poly-styrene, butadiene-styrene copolymers, acrylonitrile-buta-diene-styrene copolymers, polyethylene terephthalate and unsaturated polyesters.
The compounds of formula (I) may be used in mix-ture with the synthetic polymers in various proportions depending on the nature of the polymer, the final use and the presence of other additives. In general, it is appropriate to use 0.01 to 5% by weight of the compounds of formula (I) relative to the weight of the polymers, and preferably 0.1 to 1%.
The compounds of formula (I) may be incorporated into the polymer materials by various methods such as dry `
mixing in powder form, or wet mixing in the form of a solu-tion or suspension or in the form of a master batch. In such operations, the synthetic polymer may be used in the form of ;~
powder, granules, solution, suspension or emulsion. The poly~
mers stabilized by means of products of formula (I) may be `
used for preparing moulded objects, films, stretched tapes, fibres, monofilaments and the like.
Other additives may be added, if required, to the mixtures of the compounds of formula (I) and the synthetic polymers, such as anti-oxidan~s, UV absorbers, nickel stabi-lizers, pigments, fillers, plasticisers, antistatic agents, flame retardants, lubricating agents, corrosion protectors and metal deactivators. Examples of additives which may be ;~
used in mixture with the compounds of formula (I) are, ip particular~
phenolic anti-oxidants, such as 2,6-di-tert-butyl-p-cresol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)-butane, octadecyl 3- --(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerithritol tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (3,5-di-tert-butyl-4-hydrQxybenzyl) isocyanate;
thiodipropionic acid ~sters such a~ di-n-dodecylthiodipropio-nate, di-n-octadecyl thiodipropionate;
Aliphatic sulphides and disulphides such as di-n-dodecyl sul-phide, di-n-octadecyl sulphide, di-n -octadecyl disulphide;
aliphatic, aromatic or aliphatic-aromatic phosphites and thio-phosphites, such as tri-n-dodecyl phosphite, tri(nonyl-phenyl) phospite, tri-n-dodecyl trithiophosphite, phneyl di-n-decyl phosphite, di-n-octadecyl pentaerithritol diphosphite;
W absorbers such as 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-(2'-hydroxy-3',5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl) benzotriazole, 2,4-ditert-butylphenyl :
9~
R3 4 :
-~ - R5 (II) R6 7 :
in which R3, R4, R6 ~ R7, which are the same or equal, each represent an alkyl containing 1 to 6 C and R5 represents H, O, an alkyl of 1-12 C, an alkenyl or alkinyl of 2-12C; X, Y, which are the same or different, each represent -O-, -S-, -N- ~ R8 being H or a linear or branchPd alkyl containing 1 to 18 C, a cycloalkyl containing 5-18 C, an aryl containing ~;
6-18 C, an aryl alkyl containing 7-18 C, or a piperidine radi-cal of formula (II~.
The radicals Rl-X-, R2-Y- may also represent radicals 10 of nitrogenated heterocyclic compounds of 5-8 terms joined to ~ -the triazine ring by one atom of nitrogen of said radical, and n is a whole number between 7 and 2000.
Z represents an n-valent radical obtained by elimi-nating n active hydrogen atoms from linear or branched poly- ~ :
amines containing at least 7 primary and/or secondary amino ~
groups, for example polyamines containing repetitive units of ~ I
the type;
-N-Rg- (III) :~
H
or -N-Rg-N-Rlo~ (IV) : ~:
H H ;~
20 or -N-Rg-N-Rlo~ (V) H ,Rll or -CH2-~H- (VI) ~ ~
(CH2)m ~ ~`
NH R12 :~
--3-- ::
in which Rg, R1o, Rll which may be the same or diEferent, each represent a 2-12 C alkylene, a 5-12 C cycloalkylene, a 6-12 C
arylene,a 7-12 C arylalkylene or a -CH2-CH-CH2- radical.
OH
R12 is hydrogen, a 1-12 C linear or branched alkyl, a 5-12 C cycloalkyl, a substituted or unsubstituted 6-12 C
aryl, or a 7-12 C aryl alkyl, and m is zero or 1.
In formula (I), there must be at least one piperi-dine radical of formula (II) present in the Rl-X- or R2-Y-radicals.
Examples of Rl, R2, besides H, are methyl, ethyl, isopropyl, n-butyl, isobutyl, n~hexyl, n-octyl, n-dodecyl, n-octadecyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, phenyl, o-, m-, p-toluyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, ~ -`
a or ~-naphthyl, benzyl, p-methylbenzyl, 2,2,6,6-tetramethyl- -4-piperidyl, 1,2,2,6,6-pentamethyl-4-piperidyl, l-allyl-2,2,6,6-tetramethyl-4-piperidyl.
Examples of R3, R4, R6, R7 are methyl, ethyl, n-propyl, n-butyl, n-hexyl.
Examples of R5, besides hydro~en, are methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-dodecyl, allyl, and propinyl. ~-Examples of X and Y are -O-, -S-, -N-, where R8 besides hydrogen may be methyl, ethyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, n-octadecyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, phenyl, p-toluyl, benzyl, 2,2,6,6- - ~
tetramethyl-4-piperidyl, 1,2,2,6,6-pentamethyl-4-piperidyl, ~ ;
, l-ethyl-2,2,6,6-tetramethyl-4-piperidyl, or 1-n-propyl-2,2,6,6-tetramethyl-4-piperidyl.
The radicals Rl-X-, R2-Y- may also represent radi-cals of 5 to 8 term nitrogenated heterocyclic compounds such as l-pyrrolidinyl, l-piperidinyl, 4-morpholinyl, 4-methyl-1-piperazinyl, 4-methyl-1-homopiperazinyl. `~ ~ ;
:` ' .
-4- `~
1 f R R R are ethylene, 1,2-propylene, trimethylene, hexamethylene, 2,2,4-trimethylhexamethylene, ~ 2,4,4-trimethylhexamethylene, decamethylene, 1,4-cyclohexylene, tr 4,4'-methylene-dicyclohexylene, o-, m-, p-phenylene, o-, m-, p-xilylene, and 2-hydroxy-1,3-propyle~le.
Examples of polyamines containing repetitive units of types (III), (IV), (V) are those polyethyleneimines ob-tained by cationic polymerization of ethyleneimine (Kir~-Othermer Encycl. of Chem. Tech. vol. 17, 406), or those poly-10 amines obtained for example by reacting a primary diamine with a dihaloalkane (see for example Belgium Patent 614,619 and Japanese Patent 10,534/60) or a dihalocycloalkane, or a dihalo-arene, or a dihaloalkarene, or with epichlorohydrine (see for example British Patent 950,852). Examples of polyamines con-taining repetitive units of type (VI) are polyvinylamine (see for example British Patent 772,345) and polymerR and copolymers of allylamine (see for example U. S. A. Patent 3,057,833).
Preparation ~ ;
The triazine compounds of formula (I) may be prepa~
red by reacting a 4,6 disubstitute~ 2-halo-1,3,5-triazine of formula (VII):
N (VII) Rl~ X ~ ~ - halogen N
R2 ;
in which the halogen is preferably chlorine, with polyamines `~
characterized by a repetitive unit of the type: ~`
-N-Rg- (III) ` -~
H
or -N-Rg-N-Rlo~ (IV) H H
or -N-R -N-R - (V) H ,R11 -5- ; `
~IV~
or -C~2-CH- (VI) (CH2)m In the reaction between the reactants of formula (VII) and the polyamines it is preferable to use 1 mole of intermediate (VII) for each NH or NH2 group. However, it is possible to use a smaller quantity of reactant (VII), for example 0.1 to 1 mole for each NH or NH2 group of polyamines, but it is also possible to use an excess of reactant (VII).
The reactions between the halotriazines (VII) and `~
polyamines are conducted preferably in the presence of inert solvents such as acetone, dioxane, toluene, or xylene, working generally at the solvent boiling point.
The reactions are carried out in the presence of organic and inorganic bases for fixing the liberated halogen acid. Triethylamine, tributylamine, sodium hydrate, carbo-nate or bicarbonate, or potassium hydrate or carbonate may ~ `~
for example be used.
In order to better illustrate the present invention,some examples of preparation of the compounds according to the invention are given hereinafter, these examples being given only as non-limiting illustrations. ~;
A) Preparation of 2-chloro-4,6-bis-lN(2,2,6,6-tetramethyl-4-piperidyl)-butylamino~-1,3,5-triazine.
212 g (1 mole) of 2,2,6,6-tetramethyl-4-n-butylamino- ~`
piperidine dissolved in 100 ml of acetone are added to a mix-ture of 92.25 g (0.5 moles) of cyanuric chloride, 700 ml of ~ `
acetone and 600 g of ice. The temperature of the mixture is ~-raised to 35C, then 40 g (1 mole) of sodium hydrate dissolved ~ ' ~;'' ~ ~ -... . .
., ~ in 400 ml of water are added.
; The mixture is agitated for 6 hours at 35-40C. The pre-cipitate obtained is filtered, washed with water and dried over anhydrous CaC12. After crystallization from xylol, a white crystalline powder is obtained having a melting point of 83-85C.
Chlorine = 6,48% (calculated for C29H54ClN7 - 6.62%).
B) Preparation of the poly -(2.4-bis[N(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl¦- derivative of polyethylenimine of molecular weight 450-750.
198 g (0.37 moles) of 2-chloro-4,6-bis-[N(2,2,6,6-tetramethyl-4-piperidyl)-n-butylaminoJ-i,3,5-triazine, 21.5 g of polyethyl-eneimine of molecular weight 450-750, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are heated under reflux `
for 16 hours, under agitation. After filtration, followed by evaporation of the solvent at 120C under reduced pressure (13 mm.Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 120-135C, -N - 20.58%, Cl - 0.17%. The IR spectrum for the product indicates the disappearance of ~.
the primary and secondary amino groups present in the initial polyamine.
Preparation of the poly (2,4-bis[N(2,2,6,6~
tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl)-derivative of polymethyleneimine of molecular weight 1050-1350.
198 g (0.37 moles) of 2-chloro-4,6-bis-[N(2,2,6,6-tetramethyl-4-pipexidyl)-n-butylamino]-1,3,5-triazine, 21.5 g . :: . . .
of polyethyleneimine of molecular weight 1050-135Q, 14.8 g ;~ ~
. -.~ ~. ,, .:
(0.37 moles) of sodium hydrate and 500 ml of xilene are heated `
': ` ' '`' ~'' ~' -7- - ; ~
under reflux for 16 hours, under agitation. After filtering and then evaporating the solvent at 120C under reduced pres-sure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 131-143C, N = 20.71%, Cl =
0.12%. The IR spectrum for the product indicates the disap-pearance of the primary and secondary amino groups present in the intitial polyamine.
EXAMPLE 3 -~
Preparatio~ of the poly (2,4-bis[N-(2,2,6,6-tetra-mèthyl-4-piperidyl)-n-butylamino3-1,3,5-triazin-6-yl- deriva-tive of polyethyleneimine of molecular weight 1650-1950.
198 g (0.37 moles) of 2-chloro-4,6-bis-[N-~2,2,6,6-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 1650-1950, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are heated under reflux for 16 hours, under agitation.
After filtering and then evaporating the solvent at 120C under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 161-175C, N = 20.38~, Cl = 0.23%. The IR spectrum for the product indicates the disappearance of the primary and secon-dary amino groups present in the initial polyamine.
EXAMPLE 4 `
A) Preparation of 2-chloro-4,6-bis[N(2,2,6,6-tetramethyl-4-piperidyl)ethylamino]-1,3,5-triazine.
184 g (1 mole) of 2,2,6,6-tetramethyl-4-ethylamino- '~
piperidine dissolved in 100 ml of acetone are added to a ~ ~;
mixture of 92.25 g (0.5 moles) of cyanuric chloride, 500 ml ~ `~
of acetone and 160 g of ice.
The mixture temperature is raised to 35C, and then :,, 40 g (1 mole) of sodium hydrate dissolved in 100 ml of water are added.
The mixture is agitated for 6 hours at 35-40C, the precipitate is filtered, washed with water and dried over anhydrous CaC12. On crystal~ization from acetone, a white crystalline powder is obtained which melts at 127-129C.
Chlorine - 7.36~ (calculated for C25H46ClN7 = 7.40%).
B) Preparation of the poly (2,4-bis[N(2,2,6,6-tetramethyl-4-piperidyl)ethylamino]-1,3,5-triazin-6-yl) deri-vative of polyethyleneimine of molecular weight 450-750.
177.4 g (0.37 moles) of 2-chloro-4,6-bis[N-(2,2,6,6-tetramethyl-4-piperidyl)-ethylamino]-1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 450-750, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are refluxed for 16 hours under agitation. After filtering and then evapora-ting the solvent at 120C under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtai-ned. M.P. = 168-179C; N = 23.07%; Cl = 0.15%. The IR
spectrum for the product`indicated the disappearance of the `~
primary and secondary amino groups present in the initial polyamine.
Preparation of the poly (~,4-bis[N(2,2,6,6-tetra-methyl-4-piperidyl)ethylamino]-1,3,5-triazin-6 yl) derivative of polyethyleneimine of molecular weight 1050-1350. ~`
177.4 g (0.37 mole) of 2-chloro-4,6-bis[N-(2,2,6,6- `
tetramethyl-4-piperidyl)-ethylamino]-1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 1050-1350, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are re-fluxed for 16 hours under agitation. After filtering and _ g _ -.
then evaporating the solvent at 120C under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 156-167C; N = 22.95~; Cl =
0.10%. The I.R. spectrum for the product indicates the dis-appearance of the primary and secondary amino groups present in the initial polyamine.
~ EXAMPLE 6 f A) Preparation of 2-chloro-4,6-bis(2,2,6,6-tetramethyl-4-piperidyl-amino)-1,3,5-triazine, according to ; 10 the French Patent 2.181.059. 18.45 g (0.1 moles) of cyanuric chloride are suspended in 600 ml of water and then 31.2 g ~`
(0.2 moles) of 4-amlno-2,2,6,6-tetramethylpiperidine and a ~;
solution of 8 g (0.2 moles) of sodium hydrate in 20 ml of water are added. The mixture is agitated for 30 minutes at ambient temperature and is then heated to 90C for 16 hours.
After cooling, the precipitate is separated by fil-tration, washed and dried under vacuum. A white powder is obtained with a melting point of 277-278C.
B) Preparation of the poly [2,4-bis(2,2,6,6-tetramethyl 4-piperidyl-amino)-1,3,5-triazin-6-yl] derivative of polyethyleneimine of molecular weight 450-750. i~
139.7 g (0.33 moles) of 2-chloro-4,6-bis(2,2,6,6- `~
tetramethyl-4-piperidylamino)-1,3,5-triazine, 19.3 g of poly-methy~eneimine of molecular weight 450-750, 13.2 g (0~33 - moles) of sodium hydrate and 800 ml of xylene are refluxed for 16 hours under agitation. -After filtering and then evaporating the solvent ~
at 120C under reduced pressure (15 mm Hg), a fragile resi- ~;
nous substance of light yellow colour is obtained. M.P~
172~195C; N = 25.88%; Cl = 0.25%. The IR spectrum for ~ `
-10- ~,.,~, ';`~
the product indicates the disappearance of the primary and secondary amino groups present in the initial polyamine.
A) Preparation of hexamethylenediamine-epichloro-hydrin copolymer. 580 g (5 moles) of hexamethylenediamine, 370 g (4 moles) of epichlorohydrin and 2000 ml of isopropanol are refluxed for 10 hours. During the last 8 hours 160 g (4 moles) of sodium hydrate are added in small quantities. After filtering and then evaporating the solvent at 120C under vacuum (12 mm Bg), a soft waxy substance of light yellow colour is obtained of molecular weight 800. Total N% = 17.19;
primary N% = 3.27; secondary N~ = 13.78.
B) Preparation of the poly ~2,4-bis[N-2,2,6,Ç-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl)) derivative of the hexamethylenediamine-epichlorohydrin copoly-mer of molecular weight 800.
198 g (0.37 moles) of 2-chloro-4,6-bis[N(2,2,6,6-tetramethyl-4-piperidyl)-butylamino]-1,3,5-tria2ine, 29.6 g of hexamethylenediamine-epichlorohydrin copolymer prepared as ~ ~
under A , 14.8 g (0.37 moles) of sodium hydrate and 500 ml of - ;
xylene are refluxed or 16 hours under agitation.
After filtering and then evaporating the solvent at 120C under reduced pressure (12 mm Hg), a fragile resi-nous substance of light yellow colour is obtained. M.P. =
115-130C; N = 19.12~; Cl = 0.21%. The IR spectrum for the product indicated the disapp~arance of the primary and secondary amino groups present in the initial polyamine. ~;
Compounds of formula (I) are very effective in improving the light, heat and oxidation resistance of syn- -;
thetic polymers such as high and low density polyethylene, --1 1-- .
polypropylene, ethylene-propylene copolymers, ethylene-vinylacetate copolymers, polybutadiene, polyisoprene, poly-styrene, butadiene-styrene copolymers, acrylonitrile-buta-diene-styrene copolymers, polyethylene terephthalate and unsaturated polyesters.
The compounds of formula (I) may be used in mix-ture with the synthetic polymers in various proportions depending on the nature of the polymer, the final use and the presence of other additives. In general, it is appropriate to use 0.01 to 5% by weight of the compounds of formula (I) relative to the weight of the polymers, and preferably 0.1 to 1%.
The compounds of formula (I) may be incorporated into the polymer materials by various methods such as dry `
mixing in powder form, or wet mixing in the form of a solu-tion or suspension or in the form of a master batch. In such operations, the synthetic polymer may be used in the form of ;~
powder, granules, solution, suspension or emulsion. The poly~
mers stabilized by means of products of formula (I) may be `
used for preparing moulded objects, films, stretched tapes, fibres, monofilaments and the like.
Other additives may be added, if required, to the mixtures of the compounds of formula (I) and the synthetic polymers, such as anti-oxidan~s, UV absorbers, nickel stabi-lizers, pigments, fillers, plasticisers, antistatic agents, flame retardants, lubricating agents, corrosion protectors and metal deactivators. Examples of additives which may be ;~
used in mixture with the compounds of formula (I) are, ip particular~
phenolic anti-oxidants, such as 2,6-di-tert-butyl-p-cresol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)-butane, octadecyl 3- --(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerithritol tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (3,5-di-tert-butyl-4-hydrQxybenzyl) isocyanate;
thiodipropionic acid ~sters such a~ di-n-dodecylthiodipropio-nate, di-n-octadecyl thiodipropionate;
Aliphatic sulphides and disulphides such as di-n-dodecyl sul-phide, di-n-octadecyl sulphide, di-n -octadecyl disulphide;
aliphatic, aromatic or aliphatic-aromatic phosphites and thio-phosphites, such as tri-n-dodecyl phosphite, tri(nonyl-phenyl) phospite, tri-n-dodecyl trithiophosphite, phneyl di-n-decyl phosphite, di-n-octadecyl pentaerithritol diphosphite;
W absorbers such as 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-(2'-hydroxy-3',5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl) benzotriazole, 2,4-ditert-butylphenyl :
3,5-ditert-~utyl-4-hydroxybenzoate, phenylsalicylate, p-tert-butyl-phenylsalicylate, 2,2'-dioctyloxy-5,5'-ditert-butyloxy-anylide, 2-ethoxy-5-tert-butyl-2'-ethyloxanylide;
nickel stabilizers such as Ni monoethyl 3,5-ditert-butyl-4-hydroxy-benzylphosphonate, complex butylamine-Ni 2,2~-thiobis ;20 (4-tert-octyl-phenolate), Ni 2~2'-thiobis(4-tert-octyl-phenol-phenolate), Ni dibutyl-dithiocarbamate~ Ni 3,5-ditert-butyl-
nickel stabilizers such as Ni monoethyl 3,5-ditert-butyl-4-hydroxy-benzylphosphonate, complex butylamine-Ni 2,2~-thiobis ;20 (4-tert-octyl-phenolate), Ni 2~2'-thiobis(4-tert-octyl-phenol-phenolate), Ni dibutyl-dithiocarbamate~ Ni 3,5-ditert-butyl-
4-hydroxybenzoate, Ni complex of 2-hydroxy-4-n-octyloxybenzo-phenone; organostannic compounds such as dibutyltin maleate, dibutyltin laurate, dioctyltin maleate; acrylic esters such as ethyl a-cyan-,~,~-diphenyl-acrylate, methyla-cyan-~-methyl- .:
4-methoxycinnamate;
metal salts o higher fatty acids such as calcium, barium, cadmium, zinc, lead, nickel stearates, calcium, cadmium, zinc, : .
barium laurates; organic and inorganic pigments such as Co-30 lour Index Pigment Yellow 37, Colour Index Pigment Yellow 83, :
Colour Index Pigment Red 144, Colour Index Pigment Red 48:3, ~ :
Colour Index Pigment Blue 15, Colour Index Pigment Green 7, titanium dioxide, iron oxides and the like.
-13- ~ -.
The effectiveness of the products prepared accor-ding to the invention as stabilizers is illustrated in the following examples in which the products of examplesl to 7 are used in a synthetic polyer composition.
"" '~:
,"
, ~
-13a-. ~, . . . .. . . . .. .
:. . . . . , - , . ..
; The results are compared with those obtained without using the stabilisers according to the invention and with using commer-cially obtainable known stabilisers.
2.5 g of the compounds indicated in table 1 and dis-solved in 100 ml of chloroform are mixed with 1000 g of polypro-pylene MI = 3.5, such as the powdered isotactic polypropylene sold under the trade mark Moplen C by Montedison, 1 g of n-octadecyl 3-(3,5-di-tert-butyL-4-hydroxyphenyl) propionate and 1 g of calcium stearate. The solvent is removed in an oven under vacuum at a temperature of 50C over 4 hours.
The dry mixture obtained is then extruded at a temper- ;~
ature of 200C and transformed into granules from which plates of thickness 0.2 mm are obtained by diecasting at 200C.
The plates are exposed in a Weather-Ometer 65 WR with a black pane:L temperature of 63C, and the increase in the con-tent of carbonyl groups (aco) is checked periodically, using the not-exposed samples for compensating the initial absorption of the polymer.
The time (T O.l) necessary for giving a ~CO~ = 0.1 at
4-methoxycinnamate;
metal salts o higher fatty acids such as calcium, barium, cadmium, zinc, lead, nickel stearates, calcium, cadmium, zinc, : .
barium laurates; organic and inorganic pigments such as Co-30 lour Index Pigment Yellow 37, Colour Index Pigment Yellow 83, :
Colour Index Pigment Red 144, Colour Index Pigment Red 48:3, ~ :
Colour Index Pigment Blue 15, Colour Index Pigment Green 7, titanium dioxide, iron oxides and the like.
-13- ~ -.
The effectiveness of the products prepared accor-ding to the invention as stabilizers is illustrated in the following examples in which the products of examplesl to 7 are used in a synthetic polyer composition.
"" '~:
,"
, ~
-13a-. ~, . . . .. . . . .. .
:. . . . . , - , . ..
; The results are compared with those obtained without using the stabilisers according to the invention and with using commer-cially obtainable known stabilisers.
2.5 g of the compounds indicated in table 1 and dis-solved in 100 ml of chloroform are mixed with 1000 g of polypro-pylene MI = 3.5, such as the powdered isotactic polypropylene sold under the trade mark Moplen C by Montedison, 1 g of n-octadecyl 3-(3,5-di-tert-butyL-4-hydroxyphenyl) propionate and 1 g of calcium stearate. The solvent is removed in an oven under vacuum at a temperature of 50C over 4 hours.
The dry mixture obtained is then extruded at a temper- ;~
ature of 200C and transformed into granules from which plates of thickness 0.2 mm are obtained by diecasting at 200C.
The plates are exposed in a Weather-Ometer 65 WR with a black pane:L temperature of 63C, and the increase in the con-tent of carbonyl groups (aco) is checked periodically, using the not-exposed samples for compensating the initial absorption of the polymer.
The time (T O.l) necessary for giving a ~CO~ = 0.1 at
5.85 microns is then calculated.
As a comparison, a polymer plate is prepared under the same conditions without adding the stabilisers of the pre-sent invention r plus a plate to which 2.5 g of 2-hydroxy-4-n-octyloxybenzophenone, a normal commercial stabilizer, is added.
Table 1 shows the results obtained.
.
''I . "
-14- ``
.,.
~1 ~ . : . . .
lOi~9~
Stabiliser T 0.1 (hours) Comparison test without light stabiliser 200 2-hydroxy-4-n-octyloxybenzophenone 720 Compound of example 1 1670 Compound of example 2 1620 Compound of example 3 1530 Compound of example 4 1760 Compound of example 5 1710 Compound of example 6 1870 Compound of example 7 1690 2 g of each of the compounds listed in table 2 and dissolved in 100 ml of chloroform are mixed with 1000 g of ~-high density polyethylene MI = 0.3, such as that sold by -Montedison under the trade mark Moplen RO, 0.5 g of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) ben-20 zene and 1 g of calcium stearate. ` ~ .
The solvent is removed in an oven under vacuum at a :.~ . . .
temperature of 50C over 4 hours. ~`
The dry mixture obtained is then extruded at a temper~
ature of 190C and transformed into granules from which plates ~; -of thickness 0.2 mm are obtained by diecasting at 200C.
The plates are explosed to a xenon lamp of 1500 W
such as a Xenotest 150 (trade mark) with a black panel tempera-ture of 60C and the increase in carbonyl groups (~CO) is checked periodically, using the unexposed samples to compensate ;~
the initial absorption of the polymer. The time (T 0.1) requi-red for giving a ~CO~ = 0.1 at 5.85 microns is calculated. `~
:~
-15- ~
.-,. ':
For comparison purposes, polymer plates are prepared under the same conditions:
a) without adding a light stabiliser;
b) adding 2 g of 2-hydroxy-4-n-octyloxybenzophenone;
c) adding 2 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (commercial stabiliser).
Table 2 shows the results obtained.
Stabiliser T 0.1 (hours) `
a) 370 b) 1100 ~
c) 2360 `
Compound of example 1 3080 Compound of example 2 2890 Compound of example 3 2670 Compound oE example 4 3050 Compound of example 5 2930 Compound of example 6 3170 Compound of example 7 2720 ~
,:
2 g of each of the compounds listed in table 3 are -mixed with lOOO g of low density polyethylene MI = 0.3 sold under the trade mark Pertene Z~ 5-1800, by Montedison, 0.5 g of 2,6-di-tert-butyl-p-cresol and 1 g of calcium stearate in a low speed mixer. ~ `
The mixture obtained is then extruded at 190C and transformed into granules, from which plates of thickness 0.2 - ~;
mm are obtained by diecasting at 200C, and exposed in a Xeno- ;~
test 150 (black panel temperature 60C).
. . ''' -16- ~
8~
The time (T 0.5) necessary for giving an increase in the content of carbonyl groups ~CO% = 0.5 at 5.85 microns is determined. For comparison purposes, polymer plates are prepared under the same conditions:
a) without adding light stabilizers;
b) adding 2 g of 2-hydroxy-4-n-octyloxybenzophenone;
c) adding 2 g of bis(2,2,6,6-tetrame~hyl-4-piperi-dyl) sebacate (commercial stabilizer)O -~
The results are given in table 3. ;~
TABLE 3 ~ ::
Stabilizer T 0~5 (~ours) a) 1200 ~ `
b) 2600 -~
` c) 3500 `';` `
Compound of example 1 > 5000 : ;.`
Compound of example 2 > 5000 .~
.~ ... .: .
Compound of example 3 > 5000 Compound of example 4 > 5000 : :
Compound of example 5 > 5000 Compound of example 6 > 5000 `~: .
Compound of example 7 > 5000 EXAMPLE ll ;~
5 g of the compounds indicated in table 4 are mixed ~;
as described in the previous examples with 1000 g of poly~
propylene MI = 10, 2.5 g of dioctadecyl pentaerithritol di-phosphite and 1 g of calcium stearate. :
:.The granules are transformed into fibres under the -:~
,following conditions:
., ;-. ~ , . . ~ .
I -17- `~
. ~:
;-: - . - , : : - :
ex-truder temperature 230-240C
die temperature 240C
stretching ratio l : 3 multifilament count 2270/200 den :
The fibres, mounted on a white card, are exposed until they become fragile in a Weather-Ometer 65 WR with a black panel temperature of 63C. ::~
Other samples of the same fibres are subjected to ex-traction resistance tests under the following conditions: the :.
fibres, mounted on a stainless steel frame, are immersed in an aqueous solution containing 0.5~ of a commercial detergent con-taining non-ionic and anionic surfactants such as Dixan (trade mark) sold by Henkel-Italia, kept agitated at a temperature of ~ .
80C. :: .
After 10 hours of treatment, the fibres are rinsed with distilled water, dried and exposed until they become fra-gile in a Weather-Ometer 65 WR under the conditions already :
described. ;~
As a comparison, polypropylene fibres stabilised with ~:
the following substances: ~
a) 5 g of 2-hydroxy-4-n-octyloxybenzophenone; ~ -b) 5 g of bis~2,2,6,6-tetramethyl-4-piperidyl)sebacate : :
as a replacement for the products of the present invention are prepared and treated under the same conditions. :
Table 4 shows the results obtained.
~ .:
' ~
-18- ~
Stabilizer Vntreated FibreWashed Fibre T fragility T fragility (hours) _ (hours) a) 720 250 -~-b) 1060 250 Compound of example 11290 1200 Compound of example 21210 1200 Compound of example 31250 1180 `~
Compound of example 41350 1250 Compound of example 51260 1210 Compound of example 61300 1260 Compound of example 71170 1030 ;~-5 g of the compounds indicated in Table 5 are mixed as described in the previous examples with 1000 g of polypro-pylene MI = 10, 1 g of 1,3,5-trime~hyl-2,4,6-tris(3,5di-tert-butyl-4-hydroxybenzyl) benzene (anti-oxidant) and 1 g of calcium stearate.
The granules obtained are transformed into fibres under the conditions described in Example 11.
Polypropylene fibres are prepared with the same additives but without using anti-oxidant.
The fibres obtained ara exposed until they become fragile in a forced circulation air oven kept at a temperature of 120C.
Table 5 shows the results. As a comparison, the data obtained under 5 g of a commercial stabilizer as a re-placement for the compounds of the present invention are shown.
_~ 9~
39~
. , Stabilizer Fragility Time (hours) with anti-o~idant without anti-oxidant Compound of example 1 1280 1100 Compound of example 2 1200 1130 Compound of example 3 1120 1070 Compound of example 4 960 880 Compound of example 5 1080 950 Compound of example 6 1370 1200 10Compound of example 7 930 860 :
Bis(2,2,6,6-tetramethyl-4-piperidyl~sebacate 370 320 EXAMPLE 13 ;
Polypropylene fibres are prepared as in Example 11, .
using the following additives per 10Q0 g of polymer:
- 5 g of the compound prepared as in Example 1 -~
,. . .
- 1 g of 1,3,5-tris(3,5-di-tert-butyl-4-hydrobenzyl)-1,3,5- :~
triazine-2,4,6-(lH,3Ht5H)-trione; :;
- 1 g of calcium stearate - 5 g of the pigments indicated in Table 6.
The fibres obtained are exposed until they become fragile in a Weather-Ometer 65 WR (black panel temperature 63C).
The results are given in Table 6, in comparison with `
the data obtained without the light stabilize.r.
' :~
-20- ;~` ;
~, . .
'' ,'': ''' :' - ~ lVB9~ fil Pigments Fragilitx Time (hours) Compound ex. 6 Without Light Stabilizer TiO2 anatase 1200 180 C.I. Pigment Yellow 37 1120 200 C.I. Pigment Yellow 83 1060 150 ~ ~ -C.I. Pigment Red 144 930 110 C.I. Pigment Red 48:3 980 130 -C.I. Pigment Blue 15 1300 220 C.I. Piyment Green 7 1270 250 The low density polyethylene granules prepared as described in Example 10 are transformed into plates of thick- ~
ness lmm. by diecasting at 200C. ` ;
After 48 hours at ambient temperature the appearance ;~ ~
of the plates is examined. The presence of stabilizer emer- ; -ging at the surface clearly indicates low compatibility with the polymer. ;~
The results of these observations are shown in Table ~' . . . ~
~0 7. `~
, ~, -: :
:.' ' ~':
~''; "~ , -21- ~ ~
`~
~U~9~
.
T~BLE 7 Stabilizer Appearance of the Plate Bist2,2,6,6-tetramethyl-4-piperidyl)sebacatè Plata is opaque because of the presence of stabilizer at the surface.
Compound of example 1 Bright plate (complete absence of stabilizer on surface) Compound of example 2 " : -10 Compound of example 3 " .-:
.
Compound of ~3xample 4 "
Compound of example 5 " ;~
Compound of example 6 " :
, Compound of example 7 "
~:
, ~ .
:,, .
" '"'':
~ .
'-.`.' ;;"~ ~, : . -22~
As a comparison, a polymer plate is prepared under the same conditions without adding the stabilisers of the pre-sent invention r plus a plate to which 2.5 g of 2-hydroxy-4-n-octyloxybenzophenone, a normal commercial stabilizer, is added.
Table 1 shows the results obtained.
.
''I . "
-14- ``
.,.
~1 ~ . : . . .
lOi~9~
Stabiliser T 0.1 (hours) Comparison test without light stabiliser 200 2-hydroxy-4-n-octyloxybenzophenone 720 Compound of example 1 1670 Compound of example 2 1620 Compound of example 3 1530 Compound of example 4 1760 Compound of example 5 1710 Compound of example 6 1870 Compound of example 7 1690 2 g of each of the compounds listed in table 2 and dissolved in 100 ml of chloroform are mixed with 1000 g of ~-high density polyethylene MI = 0.3, such as that sold by -Montedison under the trade mark Moplen RO, 0.5 g of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) ben-20 zene and 1 g of calcium stearate. ` ~ .
The solvent is removed in an oven under vacuum at a :.~ . . .
temperature of 50C over 4 hours. ~`
The dry mixture obtained is then extruded at a temper~
ature of 190C and transformed into granules from which plates ~; -of thickness 0.2 mm are obtained by diecasting at 200C.
The plates are explosed to a xenon lamp of 1500 W
such as a Xenotest 150 (trade mark) with a black panel tempera-ture of 60C and the increase in carbonyl groups (~CO) is checked periodically, using the unexposed samples to compensate ;~
the initial absorption of the polymer. The time (T 0.1) requi-red for giving a ~CO~ = 0.1 at 5.85 microns is calculated. `~
:~
-15- ~
.-,. ':
For comparison purposes, polymer plates are prepared under the same conditions:
a) without adding a light stabiliser;
b) adding 2 g of 2-hydroxy-4-n-octyloxybenzophenone;
c) adding 2 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (commercial stabiliser).
Table 2 shows the results obtained.
Stabiliser T 0.1 (hours) `
a) 370 b) 1100 ~
c) 2360 `
Compound of example 1 3080 Compound of example 2 2890 Compound of example 3 2670 Compound oE example 4 3050 Compound of example 5 2930 Compound of example 6 3170 Compound of example 7 2720 ~
,:
2 g of each of the compounds listed in table 3 are -mixed with lOOO g of low density polyethylene MI = 0.3 sold under the trade mark Pertene Z~ 5-1800, by Montedison, 0.5 g of 2,6-di-tert-butyl-p-cresol and 1 g of calcium stearate in a low speed mixer. ~ `
The mixture obtained is then extruded at 190C and transformed into granules, from which plates of thickness 0.2 - ~;
mm are obtained by diecasting at 200C, and exposed in a Xeno- ;~
test 150 (black panel temperature 60C).
. . ''' -16- ~
8~
The time (T 0.5) necessary for giving an increase in the content of carbonyl groups ~CO% = 0.5 at 5.85 microns is determined. For comparison purposes, polymer plates are prepared under the same conditions:
a) without adding light stabilizers;
b) adding 2 g of 2-hydroxy-4-n-octyloxybenzophenone;
c) adding 2 g of bis(2,2,6,6-tetrame~hyl-4-piperi-dyl) sebacate (commercial stabilizer)O -~
The results are given in table 3. ;~
TABLE 3 ~ ::
Stabilizer T 0~5 (~ours) a) 1200 ~ `
b) 2600 -~
` c) 3500 `';` `
Compound of example 1 > 5000 : ;.`
Compound of example 2 > 5000 .~
.~ ... .: .
Compound of example 3 > 5000 Compound of example 4 > 5000 : :
Compound of example 5 > 5000 Compound of example 6 > 5000 `~: .
Compound of example 7 > 5000 EXAMPLE ll ;~
5 g of the compounds indicated in table 4 are mixed ~;
as described in the previous examples with 1000 g of poly~
propylene MI = 10, 2.5 g of dioctadecyl pentaerithritol di-phosphite and 1 g of calcium stearate. :
:.The granules are transformed into fibres under the -:~
,following conditions:
., ;-. ~ , . . ~ .
I -17- `~
. ~:
;-: - . - , : : - :
ex-truder temperature 230-240C
die temperature 240C
stretching ratio l : 3 multifilament count 2270/200 den :
The fibres, mounted on a white card, are exposed until they become fragile in a Weather-Ometer 65 WR with a black panel temperature of 63C. ::~
Other samples of the same fibres are subjected to ex-traction resistance tests under the following conditions: the :.
fibres, mounted on a stainless steel frame, are immersed in an aqueous solution containing 0.5~ of a commercial detergent con-taining non-ionic and anionic surfactants such as Dixan (trade mark) sold by Henkel-Italia, kept agitated at a temperature of ~ .
80C. :: .
After 10 hours of treatment, the fibres are rinsed with distilled water, dried and exposed until they become fra-gile in a Weather-Ometer 65 WR under the conditions already :
described. ;~
As a comparison, polypropylene fibres stabilised with ~:
the following substances: ~
a) 5 g of 2-hydroxy-4-n-octyloxybenzophenone; ~ -b) 5 g of bis~2,2,6,6-tetramethyl-4-piperidyl)sebacate : :
as a replacement for the products of the present invention are prepared and treated under the same conditions. :
Table 4 shows the results obtained.
~ .:
' ~
-18- ~
Stabilizer Vntreated FibreWashed Fibre T fragility T fragility (hours) _ (hours) a) 720 250 -~-b) 1060 250 Compound of example 11290 1200 Compound of example 21210 1200 Compound of example 31250 1180 `~
Compound of example 41350 1250 Compound of example 51260 1210 Compound of example 61300 1260 Compound of example 71170 1030 ;~-5 g of the compounds indicated in Table 5 are mixed as described in the previous examples with 1000 g of polypro-pylene MI = 10, 1 g of 1,3,5-trime~hyl-2,4,6-tris(3,5di-tert-butyl-4-hydroxybenzyl) benzene (anti-oxidant) and 1 g of calcium stearate.
The granules obtained are transformed into fibres under the conditions described in Example 11.
Polypropylene fibres are prepared with the same additives but without using anti-oxidant.
The fibres obtained ara exposed until they become fragile in a forced circulation air oven kept at a temperature of 120C.
Table 5 shows the results. As a comparison, the data obtained under 5 g of a commercial stabilizer as a re-placement for the compounds of the present invention are shown.
_~ 9~
39~
. , Stabilizer Fragility Time (hours) with anti-o~idant without anti-oxidant Compound of example 1 1280 1100 Compound of example 2 1200 1130 Compound of example 3 1120 1070 Compound of example 4 960 880 Compound of example 5 1080 950 Compound of example 6 1370 1200 10Compound of example 7 930 860 :
Bis(2,2,6,6-tetramethyl-4-piperidyl~sebacate 370 320 EXAMPLE 13 ;
Polypropylene fibres are prepared as in Example 11, .
using the following additives per 10Q0 g of polymer:
- 5 g of the compound prepared as in Example 1 -~
,. . .
- 1 g of 1,3,5-tris(3,5-di-tert-butyl-4-hydrobenzyl)-1,3,5- :~
triazine-2,4,6-(lH,3Ht5H)-trione; :;
- 1 g of calcium stearate - 5 g of the pigments indicated in Table 6.
The fibres obtained are exposed until they become fragile in a Weather-Ometer 65 WR (black panel temperature 63C).
The results are given in Table 6, in comparison with `
the data obtained without the light stabilize.r.
' :~
-20- ;~` ;
~, . .
'' ,'': ''' :' - ~ lVB9~ fil Pigments Fragilitx Time (hours) Compound ex. 6 Without Light Stabilizer TiO2 anatase 1200 180 C.I. Pigment Yellow 37 1120 200 C.I. Pigment Yellow 83 1060 150 ~ ~ -C.I. Pigment Red 144 930 110 C.I. Pigment Red 48:3 980 130 -C.I. Pigment Blue 15 1300 220 C.I. Piyment Green 7 1270 250 The low density polyethylene granules prepared as described in Example 10 are transformed into plates of thick- ~
ness lmm. by diecasting at 200C. ` ;
After 48 hours at ambient temperature the appearance ;~ ~
of the plates is examined. The presence of stabilizer emer- ; -ging at the surface clearly indicates low compatibility with the polymer. ;~
The results of these observations are shown in Table ~' . . . ~
~0 7. `~
, ~, -: :
:.' ' ~':
~''; "~ , -21- ~ ~
`~
~U~9~
.
T~BLE 7 Stabilizer Appearance of the Plate Bist2,2,6,6-tetramethyl-4-piperidyl)sebacatè Plata is opaque because of the presence of stabilizer at the surface.
Compound of example 1 Bright plate (complete absence of stabilizer on surface) Compound of example 2 " : -10 Compound of example 3 " .-:
.
Compound of ~3xample 4 "
Compound of example 5 " ;~
Compound of example 6 " :
, Compound of example 7 "
~:
, ~ .
:,, .
" '"'':
~ .
'-.`.' ;;"~ ~, : . -22~
Claims (13)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Compounds of the general formula (I) where: R1, R2, which may be equal or different, each represent a piperidine radical of formula (II):
(II) in which R3, R4, R6, R7, which may be equal or different, each represent an alkyl containing 1 to 6 C, and R5 represents H, O, an alkyl of 1 to 12 C, an alkenyl or alkinyl of 2 to 12 C;
X, Y, which may be equal or different, each represent -?-R8, where R8 is H or a linear or branched alkyl containing 1 to 18 C, a cycloalkyl containing 5 to 18 C, a substituted or unsubstituted aryl, containing 6 to 18 C, an arylalkyl contain-ing 7 to 18 C, or a piperidine radical of formula (II);
the radicals R1-X-, R2-Y- may also represent radicals, of nitrogenated heterocyclic compounds of 5 to 8 terms joined to the triazino ring by an atom of nitrogen of said radical;
n is a whole number between 7 and 2000;
Z represents a n-valent radical obtained by elimina-ting n atoms of active hydrogen from linear or branched poly-amines containing at least 7 primary and/or secondary amino groups, for example the polyamines characterized by repetitive units of type:
(III) or (IV) or (V) or (VI) in which R9, R10 R11, which may be equal or different, each represent an alkylene of 2 to 12 C, a cycloalkylene of 5 to 12 C, an arylene of 6 to 12 C, an arylalkylene of 7 to 12 C, or a radical, R12 is hydrogen, a linear or branched alkyl of 1 to 12 C, a cycloalkyl of 5 to 12 C, a substituted or unsubstituted aryl of 6 to 12 C, an arylalkyl of 7 to 12 C, and m is zero or 1;
in formula (I) the condition that the radicals R1-X-or R2-Y- contain at least one piperidine radical of formula (II) must be satisfied.
(II) in which R3, R4, R6, R7, which may be equal or different, each represent an alkyl containing 1 to 6 C, and R5 represents H, O, an alkyl of 1 to 12 C, an alkenyl or alkinyl of 2 to 12 C;
X, Y, which may be equal or different, each represent -?-R8, where R8 is H or a linear or branched alkyl containing 1 to 18 C, a cycloalkyl containing 5 to 18 C, a substituted or unsubstituted aryl, containing 6 to 18 C, an arylalkyl contain-ing 7 to 18 C, or a piperidine radical of formula (II);
the radicals R1-X-, R2-Y- may also represent radicals, of nitrogenated heterocyclic compounds of 5 to 8 terms joined to the triazino ring by an atom of nitrogen of said radical;
n is a whole number between 7 and 2000;
Z represents a n-valent radical obtained by elimina-ting n atoms of active hydrogen from linear or branched poly-amines containing at least 7 primary and/or secondary amino groups, for example the polyamines characterized by repetitive units of type:
(III) or (IV) or (V) or (VI) in which R9, R10 R11, which may be equal or different, each represent an alkylene of 2 to 12 C, a cycloalkylene of 5 to 12 C, an arylene of 6 to 12 C, an arylalkylene of 7 to 12 C, or a radical, R12 is hydrogen, a linear or branched alkyl of 1 to 12 C, a cycloalkyl of 5 to 12 C, a substituted or unsubstituted aryl of 6 to 12 C, an arylalkyl of 7 to 12 C, and m is zero or 1;
in formula (I) the condition that the radicals R1-X-or R2-Y- contain at least one piperidine radical of formula (II) must be satisfied.
2. Compounds as claimed in Claim 1, wherein R3, R4, R6, R7 each represents a methyl, and R5 is hydrogen or methyl.
3. Compounds as claimed in Claim 1, wherein X, Y, which may be equal or different, are , where R8 is hydrogen, a linear or branched alkyl containing 1 to 10 C, a cycloalkyl containing 6 to 10 C or an aryl containing 6 to 10 C, or an arylalkyl containing 7 to 10 C or a piperidine radical of formula (II).
4. Compounds as claimed in Claim 1, wherein Z is the residue of a polyamine containing the repetitive units , or , or , or , wherein R9, R10, R11, which may be equal or different, are each a C2-C6 alkylene, a C6-C10 cycloalkylene, a C6-C10 arylene, a C7-C10 arylalkylene, or the group, R12 is hydrogen or a C1-C6 alkyl, and m is zero or 1.
5. Compounds as claimed in Claim 1, wherein X, Y are >NH or >N-alkyl of 1 to 6 C, or >N-Pip, Pip being 2,2,6,6-tetramethyl-4-piperidyl, R1, R2 are a 2,2,6,6-tetramethyl-4-piperidyl, R3, R4, R6, R7 are methyls, R5 is hydrogen, R9, R10, R11, which may be equal or different, are each a C2-C6 alkylene or the group;
R12 is hydrogen, m is 1, and n lies between 7 and 500.
R12 is hydrogen, m is 1, and n lies between 7 and 500.
6. Compounds as claimed in Claim 1, wherein Z is the residue of a linear or branched polyamine obtained by polymerizing ethyleneimine.
7. Compounds as claimed in Claim 1, wherein Z is the residue of a linear or branched polyamine obtained by conden-sing hexamethylenediamine with epichlorohydrin.
8. A process for preparing compounds of formula (I) as claimed in Claim 1, wherein a 2-halo-triazine-4,6 disubsti-tuted reacts with a polyamine containing the repetitive units or or or
9. Light and heat stabilised compositions comprising a synthetic polymer, particularly high density or low density polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polybutadiene, polyisoprene, polystyrene, butadiene-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, or polyesters, and a stabilising compound of formula (I) as claimed in Claim 1, said stabilising compound being used in a quantity lying preferably between 0.1 and 1% of the weight of the synthetic polymer.
10. Compositions as claimed in Claim 9, wherein the compounds of formula (I) are used in mixture with other addi-tives such as anti-oxidants, organic phosphites, UV absorbers, organic nickel derivatives, organostannic compounds, metal salts of higher fatty acids and pigments.
11. Compositions as claimed in Claim 9, wherein said synthetic polymer is high density or low density poly-ethylene.
12. Compositions as claimed in Claim 9, wherein said synthetic polymer is polypropylene.
13. Compositions as claimed in Claim 9, wherein said synthetic polymer is in the form of fibre, monofilament, stretched tapes, film, moulded objects and the like.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT29812 | 1976-11-26 | ||
| IT2981276A IT1123083B (en) | 1976-11-26 | 1976-11-26 | PIPERIDINE DERIVATIVES OF 1,3,5 TRIAZINE AS STABILIZERS FOR SYNTHETIC POLYMERS THAT INCLUDE THEM AND PROCEDURE FOR THEIR PREPARATION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089461A true CA1089461A (en) | 1980-11-11 |
Family
ID=11228478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA291,095A Expired CA1089461A (en) | 1976-11-26 | 1977-11-17 | Stabilisers for synthetic polymers and a process for their preparation |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5367749A (en) |
| BE (1) | BE860655A (en) |
| CA (1) | CA1089461A (en) |
| CH (1) | CH626104A5 (en) |
| DE (1) | DE2752740A1 (en) |
| ES (1) | ES464469A1 (en) |
| FR (1) | FR2372187B1 (en) |
| GB (1) | GB1580940A (en) |
| IT (1) | IT1123083B (en) |
| NL (1) | NL7712962A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4459395A (en) * | 1980-07-31 | 1984-07-10 | Chimosa Chimica Organica S.P.A. | Piperidyl derivatives of triazine copolymers, processes for their preparation and stabilized composition containing these derivatives |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234707A (en) * | 1977-11-10 | 1980-11-18 | Ciba-Geigy Corporation | Polymeric light stabilizers for plastics |
| EP0003542B1 (en) * | 1978-02-08 | 1981-11-25 | Ciba-Geigy Ag | Polyalkylpiperidine derivatives of s-triazines, their use as stabilizers for polymers and polymers thus stabilized |
| DE2961017D1 (en) * | 1979-01-29 | 1981-12-24 | Ciba Geigy Ag | Piperidyl-triazine derivatives, process for their production, their use as stabilizers for polymers and the polymers stabilized therewith |
| DE2933078A1 (en) * | 1979-08-16 | 1981-03-26 | Hoechst Ag, 65929 Frankfurt | NEW TRIAZINE DERIVATIVES, THEIR PRODUCTION AND THEIR USE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| DE2944729A1 (en) * | 1979-11-06 | 1981-05-14 | Hoechst Ag, 6000 Frankfurt | NEW TRIAZINE STABILIZERS |
| DE3022896A1 (en) * | 1980-06-19 | 1981-12-24 | Hoechst Ag, 6000 Frankfurt | POLYTRIAZINYLAMINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| DE3113455A1 (en) * | 1981-04-03 | 1982-10-21 | Hoechst Ag, 6000 Frankfurt | POLY-BIS-TRIAZINYLIMIDES, THEIR PRODUCTION, THEIR USE AS LIGHT PROTECTION AGENTS FOR POLYMERS AND THE POLYMERS STABILIZED WITH THEM |
| IT1195277B (en) * | 1981-10-02 | 1988-10-12 | Chimosa Chimica Organica Spa | PIPERIDIL DERIVATIVES OF MACROCYCLIC TRIAZIN COMPOUNDS, HAVING STABILIZING ACTIVITY FOR POLYMERS AND PROCESSES FOR THEIR PREPARATION |
| IT1152192B (en) * | 1982-05-19 | 1986-12-31 | Apital Prod Ind | COMPOUNDS FOR STABILIZING POLYMERS |
| IT1254689B (en) * | 1992-04-14 | 1995-09-28 | PIPERIDIN-TRIAZINIC COOLIGOMERS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS. | |
| GB2377709B (en) * | 1998-12-14 | 2003-06-18 | Ciba Sc Holding Ag | Sterically hindered amine compounds |
| JP2005510611A (en) * | 2001-11-30 | 2005-04-21 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | 2-Hydroxyphenyl-s-triazine crosslinking agent for polymer networks |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1393551A (en) * | 1972-04-21 | 1975-05-07 | Ciba Geigy Ag | Piperidine derivatives |
| NL179392C (en) * | 1975-03-21 | 1986-09-01 | Montefibre Spa | A METHOD FOR PREPARING STABILIZED POLYMERIC COMPOSITIONS AND A METHOD FOR PREPARING POLYAMINS SUITABLE AS A STABILIZER, AND MANUFACTURED THEREFOR. |
| IT1060458B (en) * | 1975-12-18 | 1982-08-20 | Chimosa Chimica Organica Spa | TRIAZIN PIPERIDYL COMPOUNDS SUITABLE FOR THE STABILIZATION OF SYNTHETIC POLYMERS AND PROCEDURE FOR THEIR PREPARATION |
-
1976
- 1976-11-26 IT IT2981276A patent/IT1123083B/en active
-
1977
- 1977-11-09 BE BE182490A patent/BE860655A/en unknown
- 1977-11-14 GB GB4726077A patent/GB1580940A/en not_active Expired
- 1977-11-17 CA CA291,095A patent/CA1089461A/en not_active Expired
- 1977-11-22 FR FR7735005A patent/FR2372187B1/fr not_active Expired
- 1977-11-24 JP JP14008777A patent/JPS5367749A/en active Granted
- 1977-11-24 NL NL7712962A patent/NL7712962A/en not_active Application Discontinuation
- 1977-11-25 DE DE19772752740 patent/DE2752740A1/en not_active Ceased
- 1977-11-25 ES ES464469A patent/ES464469A1/en not_active Expired
- 1977-11-25 CH CH1449177A patent/CH626104A5/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4459395A (en) * | 1980-07-31 | 1984-07-10 | Chimosa Chimica Organica S.P.A. | Piperidyl derivatives of triazine copolymers, processes for their preparation and stabilized composition containing these derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| ES464469A1 (en) | 1978-09-01 |
| GB1580940A (en) | 1980-12-10 |
| JPS5367749A (en) | 1978-06-16 |
| CH626104A5 (en) | 1981-10-30 |
| FR2372187B1 (en) | 1984-03-30 |
| BE860655A (en) | 1978-03-01 |
| FR2372187A1 (en) | 1978-06-23 |
| NL7712962A (en) | 1978-05-30 |
| IT1123083B (en) | 1986-04-30 |
| JPS62934B2 (en) | 1987-01-10 |
| DE2752740A1 (en) | 1978-06-01 |
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