CA1085835A - Polytriazine compounds - Google Patents
Polytriazine compoundsInfo
- Publication number
- CA1085835A CA1085835A CA255,636A CA255636A CA1085835A CA 1085835 A CA1085835 A CA 1085835A CA 255636 A CA255636 A CA 255636A CA 1085835 A CA1085835 A CA 1085835A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- alkyl
- hydrogen
- straight
- branched chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- C08G73/02—Polyamines
- C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
-
- 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
- C08G73/0644—Poly(1,3,5)triazines
-
- 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
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
Abstract
NOVEL POLYTRIAZINE COMPOUNDS.
ABSTRACT
Novel polytriazine compounds are produced by re-acting a dihalogen-triazine with a bifunctional compound containing amine, alcohol, mercaptan or phenol groups. The compounds are valuable light stabilizers for synthetic polymers, particularly polyolefin in the form of fibers or films.
ABSTRACT
Novel polytriazine compounds are produced by re-acting a dihalogen-triazine with a bifunctional compound containing amine, alcohol, mercaptan or phenol groups. The compounds are valuable light stabilizers for synthetic polymers, particularly polyolefin in the form of fibers or films.
Description
~ACKGR~ D ~F TIIE IlNVENTI().
Field of the invention Ihe present invention relate- tO no~el ~ol~-triazine compounds which are useful L`or improving the stability to light, heat and oxidation of polymeric substances.
Descriptlon of the prior arl It is known that synthetic polymers are liable to ~ undergo a severe deterioration of their physical and ;~ cilemical properties when they are exposed to sunlight or other ultraviolet light source.
In order to improve the stability to light of said synthetic polymers, various sta~ilizers have been pro-r j ~
.... . .
:`
," ,i' ~:: " .:
,., :. : .. ::
posed, some of which have Iound a wide commerc:ial ac-ceptance in the field, such as some benzophenones, ben-zotriazoles,aromatic salicylates,.~-cyanoacrylic acid esters,organo-tin compounds and the like, which, al-though having a certain efficiency level, are not successful to solve the problem completely, so that a need of more efficient stabilizers is very much felt in this field.
SUMMARY
:
An object of the invention is to provide new com-pounds consisting of triazine polymers havillg the fol lowing general formula:
N (I) A- -X-Rl-Y- ~ ~ -B
(,)m R2 n in which:
X, Y, Z the same or different, represent -O-, -S-, -1-.
with R3 being hydrogen, a straight or branched chain alkyl having 1 to lo C atoms, a cycloalkyl having 5 to ~:
18 C atoms, a substituted or non-substituted aryl having -~
6 to 18 C atoms, an aralkyl having 7 to 18 C atoms, S~l3~j or R3 represents a piperi~:ine rad:ical of` tht` formula:
R R
6 (II) ` R7 R8 :~ wh~rein each of R4, R5, R7 and R8 the same or different, are a Cl to C6 alkyl, and R6 is hydrogen, O, a Cl to Cl8 straight or branched chain alkyl, a C2 to Cl8 alkenyl or alkinyl, or a C7 to C18 aralkyl;
R is a C2 to C18 straight or branched chain alkylene, a C5 to Cl8 cycloalkylene, a C6 to Cl8 arylene, and a C7 to Cl8 aralkylene;
Furthermore, -X-Rl-Y- can be a bivalent radical of a heterocycle compound ~ith 6 to 8 members having 2 :
nitrogen atoms; in a such case X and Y are a dlsubsti-tuted nitrogen atom respectively;
-X-Rl-Y- can be also replaced by the radical -N -N-in which Rg, Rlo the same or different, are H, a Cl to Cl2 alkyl, a C5 to Cl2 cycloalkyl, a C6 to C12 aryl, a C7 to C12 aralkyl;
m is either zero or one;
R2 represents -H, -Cl, -Br, -OH, a straight or branched chain Cl to C18 alkyl, a C5 to C18 cycloalkyl, a substituted or not ~i5151~35 substituted C6 to C1 aryl, a C to C ~ aralkyl a ; piperidine radical of formula (II), or R2 represents the radical -N-R12, in which R11, R12 are hydrogen, C1 to C12 alkyl, C5 -to C12 cycloalkyl, C6 to C12 aryl, or C7 to C12 aralkyl;
when m is 1, the radical l~2-Z- can be the same as ~X-R1-YH, where X, Y, R1 have the meaning above indi-cated.
n is an integer from 2 to 200;
lOA and B represent the terminal groups. By the term "terminal groups" it is meant the terminal groups of a molecule of formula (I) resulting from the polymerization reaction, which generally are a residue of functional groups. The nature of said residue depends on the reaction conditions, the na-ture and amount of the reactants used in the reaction, for example, as it is known to a skilled in the art.
Said residue is preferably ll for A and -X-R1-YH for B, in that it is preferred using an excess of bi-functional compound in the reaction for controlling the molecular weight, as i-t will be more fully de-scribed later.
In formula (I) r-ules the condition that either dical -X-R~-Y- or -(Z) -X2, or both contain at least one piperidine radical of forrnula (Il).
An additional object of the invention is to provide ~' :: a method for the preparation of the above compounds of formula (I).
A further object of the invention is to provide new stabilizers for synthetic polymers for improving their stability to light, heat and oxidation.
A further object of the invention is to provide a composition of material comprising a synthetic polymer and an amount of a stabilizer of formula (I) effective to improve the weather resistance thereof, as well as additional optional additives. `~
THE DETAILED DESC~IPTION
.
In accordance with this invention, in a triazine polymer of formula (I), the following preferred embodi-ments are intended for the various substituent groups~
R3 represents hydrogen, methyl, ethyl, n-buthyl, isobu-thyl, n-octyl, 2-ethylhexyl, n-dodecyl, n-octadecyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, phenyl, o-, m-p-toluyl~ ~ or ~-naphthyl, benzyl, p-methylbenzyl,
Field of the invention Ihe present invention relate- tO no~el ~ol~-triazine compounds which are useful L`or improving the stability to light, heat and oxidation of polymeric substances.
Descriptlon of the prior arl It is known that synthetic polymers are liable to ~ undergo a severe deterioration of their physical and ;~ cilemical properties when they are exposed to sunlight or other ultraviolet light source.
In order to improve the stability to light of said synthetic polymers, various sta~ilizers have been pro-r j ~
.... . .
:`
," ,i' ~:: " .:
,., :. : .. ::
posed, some of which have Iound a wide commerc:ial ac-ceptance in the field, such as some benzophenones, ben-zotriazoles,aromatic salicylates,.~-cyanoacrylic acid esters,organo-tin compounds and the like, which, al-though having a certain efficiency level, are not successful to solve the problem completely, so that a need of more efficient stabilizers is very much felt in this field.
SUMMARY
:
An object of the invention is to provide new com-pounds consisting of triazine polymers havillg the fol lowing general formula:
N (I) A- -X-Rl-Y- ~ ~ -B
(,)m R2 n in which:
X, Y, Z the same or different, represent -O-, -S-, -1-.
with R3 being hydrogen, a straight or branched chain alkyl having 1 to lo C atoms, a cycloalkyl having 5 to ~:
18 C atoms, a substituted or non-substituted aryl having -~
6 to 18 C atoms, an aralkyl having 7 to 18 C atoms, S~l3~j or R3 represents a piperi~:ine rad:ical of` tht` formula:
R R
6 (II) ` R7 R8 :~ wh~rein each of R4, R5, R7 and R8 the same or different, are a Cl to C6 alkyl, and R6 is hydrogen, O, a Cl to Cl8 straight or branched chain alkyl, a C2 to Cl8 alkenyl or alkinyl, or a C7 to C18 aralkyl;
R is a C2 to C18 straight or branched chain alkylene, a C5 to Cl8 cycloalkylene, a C6 to Cl8 arylene, and a C7 to Cl8 aralkylene;
Furthermore, -X-Rl-Y- can be a bivalent radical of a heterocycle compound ~ith 6 to 8 members having 2 :
nitrogen atoms; in a such case X and Y are a dlsubsti-tuted nitrogen atom respectively;
-X-Rl-Y- can be also replaced by the radical -N -N-in which Rg, Rlo the same or different, are H, a Cl to Cl2 alkyl, a C5 to Cl2 cycloalkyl, a C6 to C12 aryl, a C7 to C12 aralkyl;
m is either zero or one;
R2 represents -H, -Cl, -Br, -OH, a straight or branched chain Cl to C18 alkyl, a C5 to C18 cycloalkyl, a substituted or not ~i5151~35 substituted C6 to C1 aryl, a C to C ~ aralkyl a ; piperidine radical of formula (II), or R2 represents the radical -N-R12, in which R11, R12 are hydrogen, C1 to C12 alkyl, C5 -to C12 cycloalkyl, C6 to C12 aryl, or C7 to C12 aralkyl;
when m is 1, the radical l~2-Z- can be the same as ~X-R1-YH, where X, Y, R1 have the meaning above indi-cated.
n is an integer from 2 to 200;
lOA and B represent the terminal groups. By the term "terminal groups" it is meant the terminal groups of a molecule of formula (I) resulting from the polymerization reaction, which generally are a residue of functional groups. The nature of said residue depends on the reaction conditions, the na-ture and amount of the reactants used in the reaction, for example, as it is known to a skilled in the art.
Said residue is preferably ll for A and -X-R1-YH for B, in that it is preferred using an excess of bi-functional compound in the reaction for controlling the molecular weight, as i-t will be more fully de-scribed later.
In formula (I) r-ules the condition that either dical -X-R~-Y- or -(Z) -X2, or both contain at least one piperidine radical of forrnula (Il).
An additional object of the invention is to provide ~' :: a method for the preparation of the above compounds of formula (I).
A further object of the invention is to provide new stabilizers for synthetic polymers for improving their stability to light, heat and oxidation.
A further object of the invention is to provide a composition of material comprising a synthetic polymer and an amount of a stabilizer of formula (I) effective to improve the weather resistance thereof, as well as additional optional additives. `~
THE DETAILED DESC~IPTION
.
In accordance with this invention, in a triazine polymer of formula (I), the following preferred embodi-ments are intended for the various substituent groups~
R3 represents hydrogen, methyl, ethyl, n-buthyl, isobu-thyl, n-octyl, 2-ethylhexyl, n-dodecyl, n-octadecyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, phenyl, o-, m-p-toluyl~ ~ or ~-naphthyl, benzyl, p-methylbenzyl,
2,2,6,6-tetramethyl-4-piperidyl, 1,2,2,6,6-pentamethyl-4-piperidyl, 1-ethyl-2,2,6,6-tetramethyl-4-piperidyl, l-propyl-2,2,6,6-tetramethyl-4-piperidyl.
- 5 - ;~ :
583~i Representatives of Rl are ethylene, 1,2-propylerle, trimethylene, hexamethylene, 2,2,4-trimethylhexamethy-lene, 2,4,4-trimethylhexamethylene, decamethylene, 1,4-cyclohexylene, 4,4'-methylenedicyclohexylene, o-, m-, p-phenylene, o-,m-, p-xylylene.
The radical -X-Rl-Y- can be ,,C~2-CH~ ~ 2 \ CH2-cH2-cH2\
-N ~- -N ,,,N- -N `~-\ CH -CH-' \ CH -CH2 \ CH2 - 2 or -NHNH-, -N - IN- -N N-
- 5 - ;~ :
583~i Representatives of Rl are ethylene, 1,2-propylerle, trimethylene, hexamethylene, 2,2,4-trimethylhexamethy-lene, 2,4,4-trimethylhexamethylene, decamethylene, 1,4-cyclohexylene, 4,4'-methylenedicyclohexylene, o-, m-, p-phenylene, o-,m-, p-xylylene.
The radical -X-Rl-Y- can be ,,C~2-CH~ ~ 2 \ CH2-cH2-cH2\
-N ~- -N ,,,N- -N `~-\ CH -CH-' \ CH -CH2 \ CH2 - 2 or -NHNH-, -N - IN- -N N-
3 3 C4Hg C4Hg Additionally to hydrogen, chlorine, bromine, -OH, representativeS of R2, are -NH2,-N(C~3)2, methyl, ethyl~
isopropyl, n-butyl, isobutyl, n-octyl, 1,1,3,3-tetrame-thylbutyl, n-dodecyl, n-octadecyl, cyclohexvl, 3,3,5-trimethylcyclohexyl, phenyl, 2,6-dimethylphenyl, o-, -m-, p-toluyl, ~-, or ~-naphthyl, benzyl, p-methylbenzyl, ; 2,2,6,6-tetramethyl-4-piperidyl, 1,2,2,6,6-pentamethyl-
isopropyl, n-butyl, isobutyl, n-octyl, 1,1,3,3-tetrame-thylbutyl, n-dodecyl, n-octadecyl, cyclohexvl, 3,3,5-trimethylcyclohexyl, phenyl, 2,6-dimethylphenyl, o-, -m-, p-toluyl, ~-, or ~-naphthyl, benzyl, p-methylbenzyl, ; 2,2,6,6-tetramethyl-4-piperidyl, 1,2,2,6,6-pentamethyl-
4-piperidyl, 1-ethyl-2,2,6,6-tetramethyl-4-piperidyl, 6-(2,2,6,6-tetramethyl-4-piperidylamino)-hexyl, 2-(2,2, 6,6-tetramethyl-4-piperidylamino)-ethyl.
Preparation ::
The polytriazines of the present invention can be prepared by various procedures. A first procedure is
Preparation ::
The polytriazines of the present invention can be prepared by various procedures. A first procedure is
5~3~i reacting a 2~4-dihalogen-1,3,5-triazine of forMula (III).
N
halogen ~ q -halogen (III) N~N
(,)m in which halogen is preferably chlorine, with a bifunc-tional compound (IV) 1 (IV) When in formula (I), m is one, dihalogentriazines of formula (III) can be prepared by reacting a cyanuric ha-lide, preferably chloride, with 1 mole of a compound of formula (V) R2-Z-H (V) :
An alternative procedure is reacting a cyanuric halide with a bifunctional compound of formuls (IV); depending . !
on the mole ratios in use, it is possible to obtain com-pounds according to either formula (VI~
N
_ Rl Y ~ ~
N ~ N
halogen n . (VI) or formula (VII) _ -X-R -Y ~ ~
N~N
1 n (VII) ,~.
' .. .. . . .
5~3S
The polyLriazines of formula (VI) can be .succexsively reacted with a compound of formula (V).
The reaction of the halogentriazines with the com-pounds of formula (IV) or compounds of formula (V) is carried out in the presence of an inert solvent such as acetone, dioxane, toluene, xylene, in a temperature range from -10C and the solvent boiling temperature.
The reaction is carried out in the presence of organic or inorganic bases for fixing hydrogen halide. Preferred examples of base useful to said purpose are triethyla-mine or tributylamine, sodium hydroxide, carbonate or bicarbonate, potassium hydroxide or carbonate, sodium alcoholates in the case that the compounds of formula (IV) or (V) are alcohols or glycols, sodium mercaptides in the case that the reactants of formula (IV) or (V) are mono- or di-mercaptans; it is further possible to use an amine excess, when reacting a compound of formula (VI) with a compound of formula (V), in which Z is -N-.
The mole ratio of compounds (III) to compounds (IV) can range from 1:1,5 to 1,5:1, preferably from 1:1 to 1:1,2.
When reacting a cyanuric halide with a compound (IV) to obtain products of formula (VI), the mole ratio be-tween said compounds is preferably in a range from 1:1 3~;
to 1:1,2.
When reacting a cyanur:ic halide with a compound (IV) to obtain products of formula (VII), the mole ratio be-tween said compounds is in a range from 1:2,5 to 1:2, more preferably from 1:2,4 to 1:2,1.
rarticular examples of dihalogen triazines (III) which can be employed to obtain products of formula (I), are;
2,4-dichloro-1,3,5-triazine, 2,4-dichloro-6-methyl-1,3,5-triazine, 2,4-dichloro-6-ethyl-1,3,5-triazine, 2,4-dichloro-6-phenyl-1,3,5-triazine, 2,4-dichloro-6-n-butoxy-1,3,5-triazine, 2,4-dichloro-6-n-octyloxy-1,3,5-triazine, 2,4-dichloro-6-cyclohexyloxy-1,3,5-triazine, 2,4-dichloro-6-phenoxy-1,3~5-triazine, 2,4-dichloro-6(2,6-dimethylphenoxy)1,3,5-triazine, 2,4-dichloro-6-benzyloxy-1,3,5-triazine, 2,4-dichloro-6-(2,2,6,6-tetramethyl-4-piperidyloxy) 1,395-triazine, 2,4-dichloro-6-n-octylthio-1,3,5-triazine, 2,4-dichloro-6-amino-1,3,5-triazine, 2,4-dichloro-6-n-butylamino-1,3,5-triazine, 2,4-dichloro-6-n-octylamino-1,3,5-triazine, 2,4-dichloro-6-cyclohexylamino-1,3,5-triazine, ~ s ~ ~
i83~
2,4-dichloro-6-phenylam;no-1,3,5-triazine, 2,4-dichloro-6-diethylamino-1,395-triaYiine, 2,4-dichloro-6-(2,2,6,6-tetramethyl-4-piperidylamino)-1,3,5-triazine, 2,4-dichloro-6[N(2~2,6,6-tetramethyl-4-piperidyl)--n-butylaminoJl,3,5-triazine, 2,4-dichloro-6[N(2,2,6,6-tetramethyl-4-piperidyl)--n-octylamine]1,3,5-triazine, Representatives of compounds of formula (IV) are:
hydrazine, 1,2-dimethylhydraz`ine, ethyleneglycol, 1,3-dihydroxypropane, ;
1,6-dihydroxyhexane, resorcinol, 2,2-bis (4-hydroxyphenyl~ propane, bis (3,5-dimethyl-4-hydroxyphenyl)-methane, , 1,4-bis_(hydroxymethyl)_cyclohexane, 1,2-dimercaptoethane, 2-hydroxyethylamine, ,',. 2-mercaptoethylamine, : 1,2-diaminoethane, 1,3-diaminopropane, ~-1,6-diaminohexane, 1,4-diaminocyclohexane, .. "j ~ .
3~
1,4-bis (aminomethyl) cyc:lohexane~
p-phenylenediamine, : 4,4'-diaminodiphenylmethane, p-xylylenediamine, m-xylylenediamine, 1,2-bis-(n-butylamino)-ethane, 1,6-bis-(ethylamino)-hexane, piperazine, 2,5-dimethylpiperazine,homopiperazine, 1,2-bis-(2,2,6,6tetramethyl-4-piperidylamino)-ethane, 1,3-bis-(2,2,696-tetramethyl-4-piperidylamino)-propane, 1,6-bis-(2,2,6,6-tetramethyl-4-piperidylamino)-hexane, Representatives of compounds of Eormula (V) are:
methyl-, ethyl-, n-butyl-, n-octyl , 2-ethylhexyl-, n-dodecyl-, cyclohexyl-, benzyl- alcohol; 2,2,6,6-tetra-methyl-4-piperidinol, phenol, 2,6-dimethylphenol, n-bu-tylmercaptan, n-octylmercaptan, ethylamine, n-butylamine, ~; n-octylamine, 1,1,3,3-tetramethylbutylamine, cyclohexyl-amine, 3,3,5-trimethylcyclohexylamine, aniline, p tolui- : ;
dine, benzylamine, diethylamine, di-n-butylamine, 2,2,6,6-~ tetramethyl-4-piperidylamine, 1,2,2,6,6-pentamethyl-4-;~ piperidylamine, 2,2,6,6-tetramethyl-4-n-butylaminopiper-;~ idine, 2,2,6,6-tetramethyl-4-n-octylaminopiperidine, hydra~ine, l,l-dimethyl-hydrazine, hydroxylamine.
In order to further illustrate the present invention, ' .
35i some examples of preparation are given in the following for an illustrative and not limitative purpose.
Example 1 22,1 g (0.1 moles) of 2,4-dichloro-6-n-butylamino-1,3,5-triazine, 43,34 g (0.11 moles) of 1,6-bis (2,2,
N
halogen ~ q -halogen (III) N~N
(,)m in which halogen is preferably chlorine, with a bifunc-tional compound (IV) 1 (IV) When in formula (I), m is one, dihalogentriazines of formula (III) can be prepared by reacting a cyanuric ha-lide, preferably chloride, with 1 mole of a compound of formula (V) R2-Z-H (V) :
An alternative procedure is reacting a cyanuric halide with a bifunctional compound of formuls (IV); depending . !
on the mole ratios in use, it is possible to obtain com-pounds according to either formula (VI~
N
_ Rl Y ~ ~
N ~ N
halogen n . (VI) or formula (VII) _ -X-R -Y ~ ~
N~N
1 n (VII) ,~.
' .. .. . . .
5~3S
The polyLriazines of formula (VI) can be .succexsively reacted with a compound of formula (V).
The reaction of the halogentriazines with the com-pounds of formula (IV) or compounds of formula (V) is carried out in the presence of an inert solvent such as acetone, dioxane, toluene, xylene, in a temperature range from -10C and the solvent boiling temperature.
The reaction is carried out in the presence of organic or inorganic bases for fixing hydrogen halide. Preferred examples of base useful to said purpose are triethyla-mine or tributylamine, sodium hydroxide, carbonate or bicarbonate, potassium hydroxide or carbonate, sodium alcoholates in the case that the compounds of formula (IV) or (V) are alcohols or glycols, sodium mercaptides in the case that the reactants of formula (IV) or (V) are mono- or di-mercaptans; it is further possible to use an amine excess, when reacting a compound of formula (VI) with a compound of formula (V), in which Z is -N-.
The mole ratio of compounds (III) to compounds (IV) can range from 1:1,5 to 1,5:1, preferably from 1:1 to 1:1,2.
When reacting a cyanuric halide with a compound (IV) to obtain products of formula (VI), the mole ratio be-tween said compounds is preferably in a range from 1:1 3~;
to 1:1,2.
When reacting a cyanur:ic halide with a compound (IV) to obtain products of formula (VII), the mole ratio be-tween said compounds is in a range from 1:2,5 to 1:2, more preferably from 1:2,4 to 1:2,1.
rarticular examples of dihalogen triazines (III) which can be employed to obtain products of formula (I), are;
2,4-dichloro-1,3,5-triazine, 2,4-dichloro-6-methyl-1,3,5-triazine, 2,4-dichloro-6-ethyl-1,3,5-triazine, 2,4-dichloro-6-phenyl-1,3,5-triazine, 2,4-dichloro-6-n-butoxy-1,3,5-triazine, 2,4-dichloro-6-n-octyloxy-1,3,5-triazine, 2,4-dichloro-6-cyclohexyloxy-1,3,5-triazine, 2,4-dichloro-6-phenoxy-1,3~5-triazine, 2,4-dichloro-6(2,6-dimethylphenoxy)1,3,5-triazine, 2,4-dichloro-6-benzyloxy-1,3,5-triazine, 2,4-dichloro-6-(2,2,6,6-tetramethyl-4-piperidyloxy) 1,395-triazine, 2,4-dichloro-6-n-octylthio-1,3,5-triazine, 2,4-dichloro-6-amino-1,3,5-triazine, 2,4-dichloro-6-n-butylamino-1,3,5-triazine, 2,4-dichloro-6-n-octylamino-1,3,5-triazine, 2,4-dichloro-6-cyclohexylamino-1,3,5-triazine, ~ s ~ ~
i83~
2,4-dichloro-6-phenylam;no-1,3,5-triazine, 2,4-dichloro-6-diethylamino-1,395-triaYiine, 2,4-dichloro-6-(2,2,6,6-tetramethyl-4-piperidylamino)-1,3,5-triazine, 2,4-dichloro-6[N(2~2,6,6-tetramethyl-4-piperidyl)--n-butylaminoJl,3,5-triazine, 2,4-dichloro-6[N(2,2,6,6-tetramethyl-4-piperidyl)--n-octylamine]1,3,5-triazine, Representatives of compounds of formula (IV) are:
hydrazine, 1,2-dimethylhydraz`ine, ethyleneglycol, 1,3-dihydroxypropane, ;
1,6-dihydroxyhexane, resorcinol, 2,2-bis (4-hydroxyphenyl~ propane, bis (3,5-dimethyl-4-hydroxyphenyl)-methane, , 1,4-bis_(hydroxymethyl)_cyclohexane, 1,2-dimercaptoethane, 2-hydroxyethylamine, ,',. 2-mercaptoethylamine, : 1,2-diaminoethane, 1,3-diaminopropane, ~-1,6-diaminohexane, 1,4-diaminocyclohexane, .. "j ~ .
3~
1,4-bis (aminomethyl) cyc:lohexane~
p-phenylenediamine, : 4,4'-diaminodiphenylmethane, p-xylylenediamine, m-xylylenediamine, 1,2-bis-(n-butylamino)-ethane, 1,6-bis-(ethylamino)-hexane, piperazine, 2,5-dimethylpiperazine,homopiperazine, 1,2-bis-(2,2,6,6tetramethyl-4-piperidylamino)-ethane, 1,3-bis-(2,2,696-tetramethyl-4-piperidylamino)-propane, 1,6-bis-(2,2,6,6-tetramethyl-4-piperidylamino)-hexane, Representatives of compounds of Eormula (V) are:
methyl-, ethyl-, n-butyl-, n-octyl , 2-ethylhexyl-, n-dodecyl-, cyclohexyl-, benzyl- alcohol; 2,2,6,6-tetra-methyl-4-piperidinol, phenol, 2,6-dimethylphenol, n-bu-tylmercaptan, n-octylmercaptan, ethylamine, n-butylamine, ~; n-octylamine, 1,1,3,3-tetramethylbutylamine, cyclohexyl-amine, 3,3,5-trimethylcyclohexylamine, aniline, p tolui- : ;
dine, benzylamine, diethylamine, di-n-butylamine, 2,2,6,6-~ tetramethyl-4-piperidylamine, 1,2,2,6,6-pentamethyl-4-;~ piperidylamine, 2,2,6,6-tetramethyl-4-n-butylaminopiper-;~ idine, 2,2,6,6-tetramethyl-4-n-octylaminopiperidine, hydra~ine, l,l-dimethyl-hydrazine, hydroxylamine.
In order to further illustrate the present invention, ' .
35i some examples of preparation are given in the following for an illustrative and not limitative purpose.
Example 1 22,1 g (0.1 moles) of 2,4-dichloro-6-n-butylamino-1,3,5-triazine, 43,34 g (0.11 moles) of 1,6-bis (2,2,
6,6-tetramethyl-4 piperidylamino) hexane, 8 g (0.2 moles) of ~aOH and 300 ml of toluene were refluxed for 16 hours.
After filtering to remove sodium chloride and evap-orating the solvent, a light colored resinous substance of reduced viscosity (1% in chloroform at 25C) = 0.10 was obtained.
Example 2 a) 2,4-dichloro-6k(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamin~ -lD3,5-triazine was primarily prepared as a starting compound for producing a polytriazine accord-ing to the invention.
A solution of 18.4 g (0.1 moles) of cyanuric chlo-ride in 180 ml of acetone was additioned at 0C with 21.2 g (0.1 moles) of 2,2,6,6-tetramethyl-4-n-butylami-nopiperidine dissolved in 100 ml of acetone and 4 g ofsodium hydroxide dissolved in 40 ml of water.
The precipitate so obtained was filtered after 6 hours at 0C. After drying a solid product was obtained, which was purified by distillation:b.p. 151-2/0.1, m-p- 56-58DC~ Cl% 19,65 (calculated for C16H~7C12N5: 19,72%).
3~ 3~
b) 36 g (n.l moles) of 2~4-dichloro-6[~(2~2~6~6-tetramethyl-4-piperidyl)-n-butylamino]],3,5-triazine as prepared in example 2 a), 12.7 g (0.11 moles) of hexamethylenediamine, 8 g of sodium hydroxide and 200 ml of toluene were refluxed for 16 hours.
After filtering to remove sodium chloride and evap-orating the reaction solvent a light colored resinous substance of reduced viscosity (1% in chloroform at 25C) =0.12 was obtained . lO Example_3 18.4 g (0.1 moles) of cyanurie chloride, 39.4 g (0.1 moles) of 1,6-bis(2,2,6,6-tetramethyl-4-piperidyl-amino) hexane, 8 g of sodium hydroxide and 250 ml of ~' toluene were heated 8 hours at 40C. ,~
The mixture was additioned with 26.8 g (0.1 moles) of 2,2,6,6-tetramethyl-4-n-octylamino-piperidine and 1?
4 g of sodium hydroxide and refluxed for 16 hours.
After filtering to remove sodium chloride and evap- ~
orating the reaction solvent a resinous substance of ~;
r, ~ 20 reducedviscosity (1% in chloroform at 25C) = 0.13 was ii ~"
obtained.
Exam ~ -~
a) 2,4-dichloro-6-(2,6-dimethylphenoxy)1,3,5-tria-zine, was primarily prepared as a starting compound for ~i producing a polytriazine according to the invention.
."~.,~.. ,~. . .. . .
S~35 A solution of 18.4 g (0.1 moles) of cyanur ic chloride in 200 ml of acetone was additioned at 0C with a solu-tion of 12.2 g (0.1 moles) of 2,6-dimethylphenolJ 4 g of sodium hydroxide ~0.1 moles) and 100 ml of water.
The precipitate so obtained was filtered at 0C 6 hours ~.
after.
After drying and crystallizing from hexane, a white powder was obtained melting at 114-115C, Cl% 26.18 (calculated for Cll~l9C12N3 26.29%).
b) 27 g (0.1 moles) of 2,4-dichloro-6-(2 ,6-dime-thylphenoxy)l,3,5-triazine as prepared in example 4 a), 33.8 g (0.1 moles) of 1,2-bis (2,2,6,6-tetramethyl-4-piperidylamino)-ethane, 8 g of sodium hydroxide and 250 ml of toluene were refluxed for 16 hours.
After filtering to remove sodium chloride and evap-orating the reaction solvent a resinous substance of reduced viscosity (1% in chloroform at 25C) = 0.14 was obtained.
Example 5 29.4 g (0.1 moles) of 2,4-dichloro-6-n-octylthio-19 3,5-triazine, 33.8 g (0.1 moles) of 1,2-bis-(2,2,6,6-tetramethyl-4-piperidylamino)-ethane, 8 g of sodium hydroxide and 250 ml of toluene were refluxed for 16 hours.
After filtering to remove sodium chloride and evap-3~
orating the reaction solvent, a resinous substance of reduced viscosity (1% in chloroform at 25C) = 0.17 was obtained.
Example 6 35.4 g (0.09 moles) of 1,6-bis-(2,2,6,6-tetramethyl-4-piperidylamino)-hexane, 7.36 g (0.04 moles) of cyanu-riC chloride, 4.8 g of sodium hydroxide and 250 ml of toluene were fluxed for 16 hours.
After filtering to remove sodium hydroxide and evap-orating the reaction solvent, a solid substance of reducedviscosity (1% in chloroform at 25C) = 0.10 was obtained.
Example 7 36 g (0.1 moles) of 2,4-dichloro-6[N(2,2,6,6-tetra-methyl-4-piperidyl)-n-butylaming 1,3,5-triazine as pre-pared in example 2 a) dissolved in 200 ml of acetone ~ere additioned with 100 ml of water, containing in solution 12.1 g (0.11 moles) of resorcinol and 8 g of sodium hydroxide and refluxed for 16 hours.
Acetone was removed, the precipitate was filtered, washed with water and dried.
A solid product of reduced viscosity (1% in chloroform at 25C) = 0.10 was obtained.
Example 8 A solution of 18.4 g (0.1 moles) of cyanuric chlo- `~
ride in 200 ml of toluene was additioned at 10C with '.
10~5i83S
a soluLioll of 39.4 (0,l nloles) oE 1,6~bis (2,2,6,6-tetrametllyL-4-piperi(ly:Lclmillo) hexane in 1()0 ml of tolueDe and 8 g of sodium hy(lroxide.
The mixt~lre was wal n~ed at 40C ullder stirrinK for 12 hours.
After filtering to remove sodiulll chloride and evap-orat;ng the reaction solvent, a solid substance of reduced viscosity (170 in chloroform at 25~C) = 0.16 was obtained, The products as obtained in the preparation examples are summarized in the following table 1, in which the respective substituent groups are listed according to the definition of the previously specified formula (1).
Table 1 Example 1 R2 m No.
_ . ._ _ ._ _._ _ ____ ._ 1 >N- ~ NH -(CH2)6- >N ~ NTI NH n-butyl 1 2 I NH ¦ -(CH2 6- ¦ NH ¦>N~N ~ n-butyl ¦ I
~>N{~NH ¦ -CN2) ¦>N{~NH >N{~HI n-octyl l 1 4 ~N ~ NH -(CH2)2- >N ~ NH -0- 2e6hyl- . 1 ~>N~NH -(CH2 2- >N~NH S ~ n-OCeY
6 >N~NH -(CH2 6- >N~NH >N{~NI -(CH2~<
.. . . .
35~
~xample X RL Y Z R2 m ~ ml I --r----- ~------ I
After filtering to remove sodium chloride and evap-orating the solvent, a light colored resinous substance of reduced viscosity (1% in chloroform at 25C) = 0.10 was obtained.
Example 2 a) 2,4-dichloro-6k(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamin~ -lD3,5-triazine was primarily prepared as a starting compound for producing a polytriazine accord-ing to the invention.
A solution of 18.4 g (0.1 moles) of cyanuric chlo-ride in 180 ml of acetone was additioned at 0C with 21.2 g (0.1 moles) of 2,2,6,6-tetramethyl-4-n-butylami-nopiperidine dissolved in 100 ml of acetone and 4 g ofsodium hydroxide dissolved in 40 ml of water.
The precipitate so obtained was filtered after 6 hours at 0C. After drying a solid product was obtained, which was purified by distillation:b.p. 151-2/0.1, m-p- 56-58DC~ Cl% 19,65 (calculated for C16H~7C12N5: 19,72%).
3~ 3~
b) 36 g (n.l moles) of 2~4-dichloro-6[~(2~2~6~6-tetramethyl-4-piperidyl)-n-butylamino]],3,5-triazine as prepared in example 2 a), 12.7 g (0.11 moles) of hexamethylenediamine, 8 g of sodium hydroxide and 200 ml of toluene were refluxed for 16 hours.
After filtering to remove sodium chloride and evap-orating the reaction solvent a light colored resinous substance of reduced viscosity (1% in chloroform at 25C) =0.12 was obtained . lO Example_3 18.4 g (0.1 moles) of cyanurie chloride, 39.4 g (0.1 moles) of 1,6-bis(2,2,6,6-tetramethyl-4-piperidyl-amino) hexane, 8 g of sodium hydroxide and 250 ml of ~' toluene were heated 8 hours at 40C. ,~
The mixture was additioned with 26.8 g (0.1 moles) of 2,2,6,6-tetramethyl-4-n-octylamino-piperidine and 1?
4 g of sodium hydroxide and refluxed for 16 hours.
After filtering to remove sodium chloride and evap- ~
orating the reaction solvent a resinous substance of ~;
r, ~ 20 reducedviscosity (1% in chloroform at 25C) = 0.13 was ii ~"
obtained.
Exam ~ -~
a) 2,4-dichloro-6-(2,6-dimethylphenoxy)1,3,5-tria-zine, was primarily prepared as a starting compound for ~i producing a polytriazine according to the invention.
."~.,~.. ,~. . .. . .
S~35 A solution of 18.4 g (0.1 moles) of cyanur ic chloride in 200 ml of acetone was additioned at 0C with a solu-tion of 12.2 g (0.1 moles) of 2,6-dimethylphenolJ 4 g of sodium hydroxide ~0.1 moles) and 100 ml of water.
The precipitate so obtained was filtered at 0C 6 hours ~.
after.
After drying and crystallizing from hexane, a white powder was obtained melting at 114-115C, Cl% 26.18 (calculated for Cll~l9C12N3 26.29%).
b) 27 g (0.1 moles) of 2,4-dichloro-6-(2 ,6-dime-thylphenoxy)l,3,5-triazine as prepared in example 4 a), 33.8 g (0.1 moles) of 1,2-bis (2,2,6,6-tetramethyl-4-piperidylamino)-ethane, 8 g of sodium hydroxide and 250 ml of toluene were refluxed for 16 hours.
After filtering to remove sodium chloride and evap-orating the reaction solvent a resinous substance of reduced viscosity (1% in chloroform at 25C) = 0.14 was obtained.
Example 5 29.4 g (0.1 moles) of 2,4-dichloro-6-n-octylthio-19 3,5-triazine, 33.8 g (0.1 moles) of 1,2-bis-(2,2,6,6-tetramethyl-4-piperidylamino)-ethane, 8 g of sodium hydroxide and 250 ml of toluene were refluxed for 16 hours.
After filtering to remove sodium chloride and evap-3~
orating the reaction solvent, a resinous substance of reduced viscosity (1% in chloroform at 25C) = 0.17 was obtained.
Example 6 35.4 g (0.09 moles) of 1,6-bis-(2,2,6,6-tetramethyl-4-piperidylamino)-hexane, 7.36 g (0.04 moles) of cyanu-riC chloride, 4.8 g of sodium hydroxide and 250 ml of toluene were fluxed for 16 hours.
After filtering to remove sodium hydroxide and evap-orating the reaction solvent, a solid substance of reducedviscosity (1% in chloroform at 25C) = 0.10 was obtained.
Example 7 36 g (0.1 moles) of 2,4-dichloro-6[N(2,2,6,6-tetra-methyl-4-piperidyl)-n-butylaming 1,3,5-triazine as pre-pared in example 2 a) dissolved in 200 ml of acetone ~ere additioned with 100 ml of water, containing in solution 12.1 g (0.11 moles) of resorcinol and 8 g of sodium hydroxide and refluxed for 16 hours.
Acetone was removed, the precipitate was filtered, washed with water and dried.
A solid product of reduced viscosity (1% in chloroform at 25C) = 0.10 was obtained.
Example 8 A solution of 18.4 g (0.1 moles) of cyanuric chlo- `~
ride in 200 ml of toluene was additioned at 10C with '.
10~5i83S
a soluLioll of 39.4 (0,l nloles) oE 1,6~bis (2,2,6,6-tetrametllyL-4-piperi(ly:Lclmillo) hexane in 1()0 ml of tolueDe and 8 g of sodium hy(lroxide.
The mixt~lre was wal n~ed at 40C ullder stirrinK for 12 hours.
After filtering to remove sodiulll chloride and evap-orat;ng the reaction solvent, a solid substance of reduced viscosity (170 in chloroform at 25~C) = 0.16 was obtained, The products as obtained in the preparation examples are summarized in the following table 1, in which the respective substituent groups are listed according to the definition of the previously specified formula (1).
Table 1 Example 1 R2 m No.
_ . ._ _ ._ _._ _ ____ ._ 1 >N- ~ NH -(CH2)6- >N ~ NTI NH n-butyl 1 2 I NH ¦ -(CH2 6- ¦ NH ¦>N~N ~ n-butyl ¦ I
~>N{~NH ¦ -CN2) ¦>N{~NH >N{~HI n-octyl l 1 4 ~N ~ NH -(CH2)2- >N ~ NH -0- 2e6hyl- . 1 ~>N~NH -(CH2 2- >N~NH S ~ n-OCeY
6 >N~NH -(CH2 6- >N~NH >N{~NI -(CH2~<
.. . . .
35~
~xample X RL Y Z R2 m ~ ml I --r----- ~------ I
7 0 lene I ~ ~N ~ n-butyl 11 >~ ~ rlH -(CH2~6-l>~- ~ H~ Cl 1O
Light stabilization tests The polytriazine compounds of formula (I) are useful and valuable agents for improving the stability to light, heat and oxidation of synthetic polymers such as, for examp]e, high and low density polyethylene, polypropy- I
lene, ethylene-propylene copolymers, ethylene-vinylace-tate copolymers, polybutadiene, polyisoprene, polysty-rene, styrene-butadiene copolymers, acrylonitrile-buta-diene-styrene copolymers, vinyl- and vinylidene chlo-ride polymers and copolymers, polyoxymethylene, poly-ethylene-terephthalate, nylon 66, nylon ~, nylon 12, polyurethanes, insaturated polyesters.
: The compounds of formula (I) are particularly use-ful as light stabilizers for polyolefins and more par-ticularly for polyolefin articles of manufacturing hav-ing a reduced thickness, such as fibers and films. In a surprising manner said compounds are hardly liable to be extracted from said thin articles, when brought in contact with water or an aqueous surfactant solution.
The compounds of formula (I) can be employed in a mixture with the synthetic polymers in various propor-tions, depending on the polymer nature, final use and ... . . ..
35i presence of additional additives.
Generally it is preferable to employ from 0.01 to 5% by weight of compoundsof formula (I) referred to the polymer weight, more preferably from 0.1 to 1%.
The compounds of formula (I) can be included in a ; polymeric material composition by various procedures, such as dry mixing in the form of powder, or by a wet process in the form of a solution or slurry. In said operation the synthetic polymer can be employed in the form of powder, granulate, solution, slurry or emulsion, The polymers stabilized by the products of formula can be used for the manufacture of molded articles, films, tapes, fibers, monofilaments and the like.
A mixture of compounds of formula (I) and synthetic polymers can be optionally additioned with other addi-tives, such as antioxydants, UV absorbers, nickel sta-bilizers, pigments, charges, plastifying agents, anti-static agents, flame retardants, lubricating agents, anticorrosive agents, metal inhibitors, and the like.
Particular examples of additives which can be em-! ployed in a mixture with the polytriazine compounds of formula (I) are:
phenolic antioxidants, such as 2,6-ditert-butyl-p-cresol, 4,4'-thiobis-(3-methyl-6-tertbutylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-tertbutylphenyl~butane, octadecyl-3-(3,5-ditertbutyl-4-hydroxyp~leny:l)propionate, pentaerythritol-tetra-(3,5-ditert-butyl-4-hydroxyphenyl)-propionate, tris-(3,5-ditert-butyl-4-hydroxybenzyl)iso-cyanurate;
. esters of thiodipropionic acid, such as di-n-dode-cyl thiodipropionate, di-n-octadecyl-thiodipropionate, aliphatic sulfides and disulfides, such as di-n-dode-cyl-sulfide, di-n-octadecyl-sulfide, di-n-octadecyl-disulfide; .
aliphatic, aromatic or aliphatic-aromatic phosphites and thiophosphites, such as t i-n-dodecyl-phosphite, tris-(n-nonylphenyl)phosphite, tri-n-dodecyl-trithio-phosphite 9 phenyl di-n-decylphosphite, di-n-octadecyl-pentaerithritoldiphosphite;
UV absorbers such as 2-hydroxy-4-n-octyloxybenzo-phenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-(2' hydroxy-3',5'-ditert butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, : 2,4-ditertbutylphenyl-3,5-ditertbutyl-4-hydroxybenzoate, phenyl salicylate, p-tertbutylphenyl-salicylate, 2,2'-dioctyloxy-5,5'-ditertbutyloxanilide, 2-ethoxy-5-tertbutyl-2'-ethyloxanilide;
nickel stabilizers such as Ni monoethyl-3,5-di-tert butyl-4-hydroxybenzylphosphonate, butylamine-Ni 2,2' ~:
thiobis-(4-tertoctylphenolate) complex, Ni 292'-thio-- 19 ~
~15~3~
bis-(4-tertoctylphenolphenolate), Ni dibuty]dithiocar-bamate, Ni 3,5-ditertbutyl-4-hydroxybenzoate, Ni corn-plex of 2-hydroxy-4-n octyloxybenzophenone;
organo-tin compounds, such as dibutyl-tin-maleate, dibutyl-tin-laurate, di-n-octyl-tin-maleate;
acrylic esters, such as ethyl- ~-cyano- ~, ~ -di-phenylacrylate, methyl- ~-cyano- ~-methyl-4-methoxy-cinnamate metal salts of higher fat acids, such as calcium, barium, zinc, cadmium, lead, nickel stearates, calcium cadmium, barium, zinc laurates.
In the following several examples are described, in an illustrative and not limitative way, for illus-trating the usefulness of the compounds of formula (I) obtained in examples 1 - 8, for the stabilization of synthetic polymers.
The results of the tests are listed in Tables 2, 3 and 4 and compared with tests carried out without using any stabilizer and using a known stabilizer commercially available.
Example 9 2.5 g of each of the compounds listed in Table 2 below9 dissolved in 100 ml chloroform, were mixed with 1000 g polypropylene (Moplen C, manufactured by Società
Montedison, Italy, 1 g n-octadecyl-3(3,5-ditertbutyl-*Trademark 4-hydroxyphenyl)propionate and 1 g calcium stearate.
The solvent was removed in an oven under vacuum at a temperature of 50C for 4 hours.
The dry mixture so obtained was then extruded at a temperature of 200C and made into granules, wherefrom 0.2 mm thick plates were produced by diecasting at 200C.
Said plates were exposed in a xenotest 150 appara-tus at a black panel temperature of 60C and the in-crease in the content of carbonyl groups was periodi- -cally determined using the not exposed specimens for balancing the polymer original absorption. The time (T 0.1) required to have a ~ C0% = 0.1 at 5.85 /um was then calculated.
As a comparison, a polymer plate was produced under the same conditions, but without addition of any light stabilizer, and another one with the addition of 2.5 g of 2-hydroxy-4-n-octyloxybenzophenone, a usual commer-cial stabilizer.
The results are referred in Table 20 Table 2 Stabil_izer T 0.1 (hours) None 280 2-hydroxy-4-n-octyloxybenzophenone 900 Compound of example 1 1320 Compound of example 2 1030 3S~
Compound of example 3 1170 ; Compound of example 4 1240 Compound of example 5 980 Compound of example 6 1510 Compound of example 7 1050 Compound of example 8 1180 Example 10 2 g of each of the compounds listed in Table 3 below, dissolved in 100 ml chloroform, were mixed with 1000 g of high density polyethylene (Moplen R0, manufactured by Società Montedison, Italy), 0.5 g of n~octadecyl-3(3,5-ditertbutyl-4-hydroxy-phenyl)propio-nate and 1 g of calcium stearate.
The solvent was removed in an oven under vacuum at a temperature of 50C for 4 hours.
The dry mixture so obtained was then extruded at a temperature of 190C and made into granules, wherefrom by diecasting plates 0.2 mm thick were produced, said plates were exposed in a Xenotest 150 apparatus 9 as in example 9.
The time T 0.05 required to have ~C0% ~ 0.05 at 5.85/um was determined.
As a comparison, under the same conditions a poly-mer plate was produced without addition of any light stabilizer and another plate was produced with addition *Trademark 193~
of 2 g oE 2-hydroxy~4-n-octyloxybellzophenone.
The results are referrecl in Table 3.
Table 3 St b'lizer T 0 05 (hours) a l _ .
None 320 2-hydroxy-4-n-octyloxybenzophenone1100 Compound of example 1 2030 Compound of example 2 1460 Compound of example 3 2180 Compound of example 4 2070 Compound of example 5 1520 Compound of example 6 2200 Compound of example 7 1710 : Compound of example 8 1890 : Example 11 The polypropylene granules produced in example 9 : were made into fibers under the following conditions:
Extruder temperature 250-260C
Die temperature 250C
Stretching ratio 1:4 Multifilament count 1020/200 den The fibers were assembled on a white pape~board and exposed until brittleness in Xenotest 150 at a black panel temperature of 60C.
Another lot of the same fibers were subjected to 33~
~ '`
tests of extraction fastness under the following con-ditions: the fibers fixed to a stainless steel frame, were soaked into an aqueous solution containing 0,5%
b.w. of a commercially available surfactant "DIXAN", under stirring at a temperature of 80C.
After 10 hours treating, the fibers were rinsed with distilled water, dried and exposed until brittle-ness to the Xenotest 150 under the same conditions as above.
As a comparison under the same conditions, polypro-pylene fibers were produced and treated with addition of 0.25~ by weight of 2-hydroxy-4-n-octyloxybenzophe-none.
The results obtained are referred in Table 4.
Table 4 Stabilizer Time to brittleness (hours) Not treated fibers Treated fibers 2-hydroxy-4-n-octyloxybenzophenone 670 360 Compound of example l 1050 860 Compound of example 2 860 750 Compound of example 3 1130 930 Compound of example 4 1170 1090 Compound of example 5 980 810 ; Compound of example 6 1230 1110 Compound of example 7 920 800 *Trademark ~8~3~3~i Compound of example 8 970 830 From the test results, a considerable increase in the time required to induce a degradation in a polymer stabilized by the invention compounds can be observed with respect to the same polymer not stabilized. Fur-thermore, clearl~ improved effects induced by the inven-tion compounds can be observed in comparison with a similar proportion of a prior art additive.
It will further appreciate from Table 4,that the stabilizers of the invention maintain a very high pro-portion of their activity, when the stabilized fibers have been treated so as to promote the extraction thereof from the polymer~ even when the polymer is in the very thin form of a fiber or film.
, ~ - 25 -
Light stabilization tests The polytriazine compounds of formula (I) are useful and valuable agents for improving the stability to light, heat and oxidation of synthetic polymers such as, for examp]e, high and low density polyethylene, polypropy- I
lene, ethylene-propylene copolymers, ethylene-vinylace-tate copolymers, polybutadiene, polyisoprene, polysty-rene, styrene-butadiene copolymers, acrylonitrile-buta-diene-styrene copolymers, vinyl- and vinylidene chlo-ride polymers and copolymers, polyoxymethylene, poly-ethylene-terephthalate, nylon 66, nylon ~, nylon 12, polyurethanes, insaturated polyesters.
: The compounds of formula (I) are particularly use-ful as light stabilizers for polyolefins and more par-ticularly for polyolefin articles of manufacturing hav-ing a reduced thickness, such as fibers and films. In a surprising manner said compounds are hardly liable to be extracted from said thin articles, when brought in contact with water or an aqueous surfactant solution.
The compounds of formula (I) can be employed in a mixture with the synthetic polymers in various propor-tions, depending on the polymer nature, final use and ... . . ..
35i presence of additional additives.
Generally it is preferable to employ from 0.01 to 5% by weight of compoundsof formula (I) referred to the polymer weight, more preferably from 0.1 to 1%.
The compounds of formula (I) can be included in a ; polymeric material composition by various procedures, such as dry mixing in the form of powder, or by a wet process in the form of a solution or slurry. In said operation the synthetic polymer can be employed in the form of powder, granulate, solution, slurry or emulsion, The polymers stabilized by the products of formula can be used for the manufacture of molded articles, films, tapes, fibers, monofilaments and the like.
A mixture of compounds of formula (I) and synthetic polymers can be optionally additioned with other addi-tives, such as antioxydants, UV absorbers, nickel sta-bilizers, pigments, charges, plastifying agents, anti-static agents, flame retardants, lubricating agents, anticorrosive agents, metal inhibitors, and the like.
Particular examples of additives which can be em-! ployed in a mixture with the polytriazine compounds of formula (I) are:
phenolic antioxidants, such as 2,6-ditert-butyl-p-cresol, 4,4'-thiobis-(3-methyl-6-tertbutylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-tertbutylphenyl~butane, octadecyl-3-(3,5-ditertbutyl-4-hydroxyp~leny:l)propionate, pentaerythritol-tetra-(3,5-ditert-butyl-4-hydroxyphenyl)-propionate, tris-(3,5-ditert-butyl-4-hydroxybenzyl)iso-cyanurate;
. esters of thiodipropionic acid, such as di-n-dode-cyl thiodipropionate, di-n-octadecyl-thiodipropionate, aliphatic sulfides and disulfides, such as di-n-dode-cyl-sulfide, di-n-octadecyl-sulfide, di-n-octadecyl-disulfide; .
aliphatic, aromatic or aliphatic-aromatic phosphites and thiophosphites, such as t i-n-dodecyl-phosphite, tris-(n-nonylphenyl)phosphite, tri-n-dodecyl-trithio-phosphite 9 phenyl di-n-decylphosphite, di-n-octadecyl-pentaerithritoldiphosphite;
UV absorbers such as 2-hydroxy-4-n-octyloxybenzo-phenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-(2' hydroxy-3',5'-ditert butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, : 2,4-ditertbutylphenyl-3,5-ditertbutyl-4-hydroxybenzoate, phenyl salicylate, p-tertbutylphenyl-salicylate, 2,2'-dioctyloxy-5,5'-ditertbutyloxanilide, 2-ethoxy-5-tertbutyl-2'-ethyloxanilide;
nickel stabilizers such as Ni monoethyl-3,5-di-tert butyl-4-hydroxybenzylphosphonate, butylamine-Ni 2,2' ~:
thiobis-(4-tertoctylphenolate) complex, Ni 292'-thio-- 19 ~
~15~3~
bis-(4-tertoctylphenolphenolate), Ni dibuty]dithiocar-bamate, Ni 3,5-ditertbutyl-4-hydroxybenzoate, Ni corn-plex of 2-hydroxy-4-n octyloxybenzophenone;
organo-tin compounds, such as dibutyl-tin-maleate, dibutyl-tin-laurate, di-n-octyl-tin-maleate;
acrylic esters, such as ethyl- ~-cyano- ~, ~ -di-phenylacrylate, methyl- ~-cyano- ~-methyl-4-methoxy-cinnamate metal salts of higher fat acids, such as calcium, barium, zinc, cadmium, lead, nickel stearates, calcium cadmium, barium, zinc laurates.
In the following several examples are described, in an illustrative and not limitative way, for illus-trating the usefulness of the compounds of formula (I) obtained in examples 1 - 8, for the stabilization of synthetic polymers.
The results of the tests are listed in Tables 2, 3 and 4 and compared with tests carried out without using any stabilizer and using a known stabilizer commercially available.
Example 9 2.5 g of each of the compounds listed in Table 2 below9 dissolved in 100 ml chloroform, were mixed with 1000 g polypropylene (Moplen C, manufactured by Società
Montedison, Italy, 1 g n-octadecyl-3(3,5-ditertbutyl-*Trademark 4-hydroxyphenyl)propionate and 1 g calcium stearate.
The solvent was removed in an oven under vacuum at a temperature of 50C for 4 hours.
The dry mixture so obtained was then extruded at a temperature of 200C and made into granules, wherefrom 0.2 mm thick plates were produced by diecasting at 200C.
Said plates were exposed in a xenotest 150 appara-tus at a black panel temperature of 60C and the in-crease in the content of carbonyl groups was periodi- -cally determined using the not exposed specimens for balancing the polymer original absorption. The time (T 0.1) required to have a ~ C0% = 0.1 at 5.85 /um was then calculated.
As a comparison, a polymer plate was produced under the same conditions, but without addition of any light stabilizer, and another one with the addition of 2.5 g of 2-hydroxy-4-n-octyloxybenzophenone, a usual commer-cial stabilizer.
The results are referred in Table 20 Table 2 Stabil_izer T 0.1 (hours) None 280 2-hydroxy-4-n-octyloxybenzophenone 900 Compound of example 1 1320 Compound of example 2 1030 3S~
Compound of example 3 1170 ; Compound of example 4 1240 Compound of example 5 980 Compound of example 6 1510 Compound of example 7 1050 Compound of example 8 1180 Example 10 2 g of each of the compounds listed in Table 3 below, dissolved in 100 ml chloroform, were mixed with 1000 g of high density polyethylene (Moplen R0, manufactured by Società Montedison, Italy), 0.5 g of n~octadecyl-3(3,5-ditertbutyl-4-hydroxy-phenyl)propio-nate and 1 g of calcium stearate.
The solvent was removed in an oven under vacuum at a temperature of 50C for 4 hours.
The dry mixture so obtained was then extruded at a temperature of 190C and made into granules, wherefrom by diecasting plates 0.2 mm thick were produced, said plates were exposed in a Xenotest 150 apparatus 9 as in example 9.
The time T 0.05 required to have ~C0% ~ 0.05 at 5.85/um was determined.
As a comparison, under the same conditions a poly-mer plate was produced without addition of any light stabilizer and another plate was produced with addition *Trademark 193~
of 2 g oE 2-hydroxy~4-n-octyloxybellzophenone.
The results are referrecl in Table 3.
Table 3 St b'lizer T 0 05 (hours) a l _ .
None 320 2-hydroxy-4-n-octyloxybenzophenone1100 Compound of example 1 2030 Compound of example 2 1460 Compound of example 3 2180 Compound of example 4 2070 Compound of example 5 1520 Compound of example 6 2200 Compound of example 7 1710 : Compound of example 8 1890 : Example 11 The polypropylene granules produced in example 9 : were made into fibers under the following conditions:
Extruder temperature 250-260C
Die temperature 250C
Stretching ratio 1:4 Multifilament count 1020/200 den The fibers were assembled on a white pape~board and exposed until brittleness in Xenotest 150 at a black panel temperature of 60C.
Another lot of the same fibers were subjected to 33~
~ '`
tests of extraction fastness under the following con-ditions: the fibers fixed to a stainless steel frame, were soaked into an aqueous solution containing 0,5%
b.w. of a commercially available surfactant "DIXAN", under stirring at a temperature of 80C.
After 10 hours treating, the fibers were rinsed with distilled water, dried and exposed until brittle-ness to the Xenotest 150 under the same conditions as above.
As a comparison under the same conditions, polypro-pylene fibers were produced and treated with addition of 0.25~ by weight of 2-hydroxy-4-n-octyloxybenzophe-none.
The results obtained are referred in Table 4.
Table 4 Stabilizer Time to brittleness (hours) Not treated fibers Treated fibers 2-hydroxy-4-n-octyloxybenzophenone 670 360 Compound of example l 1050 860 Compound of example 2 860 750 Compound of example 3 1130 930 Compound of example 4 1170 1090 Compound of example 5 980 810 ; Compound of example 6 1230 1110 Compound of example 7 920 800 *Trademark ~8~3~3~i Compound of example 8 970 830 From the test results, a considerable increase in the time required to induce a degradation in a polymer stabilized by the invention compounds can be observed with respect to the same polymer not stabilized. Fur-thermore, clearl~ improved effects induced by the inven-tion compounds can be observed in comparison with a similar proportion of a prior art additive.
It will further appreciate from Table 4,that the stabilizers of the invention maintain a very high pro-portion of their activity, when the stabilized fibers have been treated so as to promote the extraction thereof from the polymer~ even when the polymer is in the very thin form of a fiber or film.
, ~ - 25 -
Claims (56)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound having the formula (I):
(I) wherein X, Y, Z, the same or different, is a member selected from - O -, - S -, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different are members selected from C1 to C6 alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, C2 to C18 alkenyl or alkynyl, C7 to C18 aralkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C18 arylene, C7 to C18 aralkylene;
R2 is selected from hydrogen, chlorine, bromine, - OH, C1 to C18 straight or branched chain alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II), a group wherein R11, R12 are selected from hydrogen or C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aral-kyl;
m is an integer from 0 to 1;
n is an integer form 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or - X - R1 - YH:
or where - XR1 - Y - represent a bivalent hetero-cyclic group having 6 to 8 nitrogen atoms with X and y each representing a disubstituted nitrogen atom;
or where - X - R1 - Y - represent a residue in which R9 and R10 are hydrogen, C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, or C7 to C12 aralkyl;
with the proviso that at least one of the radicals - X - R1 - Y and - (Z)m - R2 contains a piperidine radical of formula (II).
(I) wherein X, Y, Z, the same or different, is a member selected from - O -, - S -, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different are members selected from C1 to C6 alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, C2 to C18 alkenyl or alkynyl, C7 to C18 aralkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C18 arylene, C7 to C18 aralkylene;
R2 is selected from hydrogen, chlorine, bromine, - OH, C1 to C18 straight or branched chain alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II), a group wherein R11, R12 are selected from hydrogen or C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aral-kyl;
m is an integer from 0 to 1;
n is an integer form 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or - X - R1 - YH:
or where - XR1 - Y - represent a bivalent hetero-cyclic group having 6 to 8 nitrogen atoms with X and y each representing a disubstituted nitrogen atom;
or where - X - R1 - Y - represent a residue in which R9 and R10 are hydrogen, C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, or C7 to C12 aralkyl;
with the proviso that at least one of the radicals - X - R1 - Y and - (Z)m - R2 contains a piperidine radical of formula (II).
2. A compound according to claim 1 having the formula (I):
(I) wherein X, Y, Z, the same or different, is a member selected from - O -, - S -, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II) (II) wherein R4, R5, R7, R8, the same or different, are members selected from C1 to C6 alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, C2 to C18 alkenyl or alkynyl, C7 to C18 aralkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C18 arylene, C7 to C18 aralkylene;
R2 is selected from hydrogen, chlorine, bromine, OH, C1 to C18 straight or branched chain alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of form-ula (II), a group wherein R11, R12 are selected from hydrogen or C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aral-kyl;
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or - X - R1 - YH;
in formula (I) the condition there is that at least one of the radicals - X - R1 - Y - and - (Z) - R2 contains a piperidine radical of formula (II).
(I) wherein X, Y, Z, the same or different, is a member selected from - O -, - S -, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II) (II) wherein R4, R5, R7, R8, the same or different, are members selected from C1 to C6 alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, C2 to C18 alkenyl or alkynyl, C7 to C18 aralkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C18 arylene, C7 to C18 aralkylene;
R2 is selected from hydrogen, chlorine, bromine, OH, C1 to C18 straight or branched chain alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of form-ula (II), a group wherein R11, R12 are selected from hydrogen or C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aral-kyl;
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or - X - R1 - YH;
in formula (I) the condition there is that at least one of the radicals - X - R1 - Y - and - (Z) - R2 contains a piperidine radical of formula (II).
3. A compound according to claim 2, wherein - X - R1 -Y - represents a bivalent radical of a heterocyclic compound having 6 to 8 members, containing 2 nitrogen atoms, X and Y each representing a disubstituted nitrogen atom.
4. A compound according to claim 2, wherein the group - X - R1 - Y - represents a residue in which R9 and R10, the same or different are members selected from hydrogen, C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aralkyl.
5. A compound according to claim 2, wherein m is one and the radical R2 - Z - is the same as - X - R1 - YH.
6. A compound according to claim 2, wherein R3 is select-ed from hydrogen, C1 to C12 straight or branched chain alkyl, and a piperidine radical of formula (II).
7. A compound according to claim 2, wherein R1 is select-ed from straight or branched chain C2 to C10 alkylene, and C6 to C10 arylene.
8. A compound according to claim 2, wherein R2 is sel-ected from hydrogen, a C1 to C12 straight or branched chain alkyl, and a piperidine radical of formula (II).
9. A compound according to claim 2, wherein the radical R2 - Z - is Pip being the radical of formula (II).
10. A compound according to claim 2, wherein A is hydrogen and B is - X - R1 - YH.
11. A compound according to claim 9, wherein A is hydrogen and B is
12. A compound according to claim 2, wherein R4, R5, R7, R8 are each methyl and R6 is hydrogen or methyl.
13. A compound according to claim 2, wherein R1 is C2 to C10 alkylene or C6 to C8 arylene;
R2 is H, C4 to C12 alkyl or piperidyl of formula (II);
R3 is H, C4 to C12 alkyl or piperidyl of formula (II);
R4, R5, R7 and R8 are methyl;
R6 is hydrogen or methyl;
R9, R10, R11, R12 are hydrogen;
X, Y, Z represents -O-, -NH-, or Pip being a piperidyl of formula (II);
A is H;
B is r being an integer from 2 to 6;
m is 0 to 1;and n is an integer from 2 to 100.
R2 is H, C4 to C12 alkyl or piperidyl of formula (II);
R3 is H, C4 to C12 alkyl or piperidyl of formula (II);
R4, R5, R7 and R8 are methyl;
R6 is hydrogen or methyl;
R9, R10, R11, R12 are hydrogen;
X, Y, Z represents -O-, -NH-, or Pip being a piperidyl of formula (II);
A is H;
B is r being an integer from 2 to 6;
m is 0 to 1;and n is an integer from 2 to 100.
14. A synthetic polymer of increased stability having in-corporated with the polymer an amount of a compound according to claim 1 effective to increase the light stability of the polymer.
15. A composition according to claim 14 wherein -XR1-Y-represent a bivalent heterocyclic group having 6 to 8 nitrogen atoms with X and Y each representing a disubstituted nitrogen atom or where -X-R1-Y- represent a residue
16. A composition according to claim 14, wherein said synthetic polymer is a polyolefin.
17. A composition according to claim 16, wherein said synthetic polymer is polypropylene.
18. A composition according to claim 16, wherein said synthetic polymer is polyethylene.
19. A composition according to claim 16, wherein said synthetic polymer is in the form of fibers or film.
20. A composition according to claim 14, wherein said compound is added to the synthetic polymer composition in an amount from 0.1 to 1% by weight referred to the synthetic polymer composition.
21. A synthetic polymer of increased stability having in-corporated with the polymer an amount of a compound according to claim 2 effective to increase the light stability of the polymer.
22. A method of producing a compound having the general formula (I):
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from C1 to C6 alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, C2 to C18 alkenyl or alkynyl, C7 to C18 aralkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C18 arylene, C7 to C18 aralkylene;
R2 is selected from hydrogen, chlorine, bromine, -OH
C1 to C18 straight or branched chain alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of form-ula (II), a group wherein R11, R12 are selected from hydrogen or C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aral-kyl;
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) there is the condition that at least one of the radicals -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II), comprising reacting a compound of formula (IV):
HX - R1 - YH (IV) X, Y, R1 having the meaning as previously defined, with a member of the group consisting of (a) 2,4-dihalogentriazines of formula (III) (III) and (b) cyanuric halide in solution in inert solvent, at a temper-ature, in the presence of an organic or inorganic base.
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from C1 to C6 alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, C2 to C18 alkenyl or alkynyl, C7 to C18 aralkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C18 arylene, C7 to C18 aralkylene;
R2 is selected from hydrogen, chlorine, bromine, -OH
C1 to C18 straight or branched chain alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of form-ula (II), a group wherein R11, R12 are selected from hydrogen or C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aral-kyl;
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) there is the condition that at least one of the radicals -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II), comprising reacting a compound of formula (IV):
HX - R1 - YH (IV) X, Y, R1 having the meaning as previously defined, with a member of the group consisting of (a) 2,4-dihalogentriazines of formula (III) (III) and (b) cyanuric halide in solution in inert solvent, at a temper-ature, in the presence of an organic or inorganic base.
23. The method according to claim 22, comprising reacting 2,4-dihalogentriazines of formula (III) with a compound of formula (IV) in a molar ratio from 1:1.5 to 1.5:1.
24. A method according to claim 22, in which said halogen is chlorine.
25. A method according to claim 22, comprising reacting a cyanuric halide with a compound of formula (IV) in a molar ratio from 1:1 to 1:1.2, to obtain a product having the formula (VI) (VI) (VI) in which m is as defined in formula (I) is zero.
26. A method according to claim 25, wherein said product (VI) is successively reacted with a compound of formula (V) to obtain a product of formula (I) in which m is 1.
27. A method according to claim 22, comprising reacting a cyanuric halide with a compound of formula (IV) in a molar ratio from 1:2.4 to 1:2.1 to obtain a product of formula (VII) (VII) (VII)
28. A method of increasing the light stability of a synthetic polymer, comprising adding to a composition of material of said synthetic polymer, an amount of a compound having the formula (I):
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from C1 to C6 alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, C2 to C18 alkenyl or alkynyl, C7 to C18 aralkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C18 arylene, C7 to C18 aralkylene;
R2 is selected from hydrogen, chlorine, bromine, -OH, C1 to C18 straight or branched chain alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II), a group wherein R11, R12 are selected from hydrogen or C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aralkyl;
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) ruling the condition that at least one of the radicals -X-R1-Y- and -(Z) -R2 contains a piperidine radical of formula (II), effective to increase the light stability of said synthetic polymer.
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from C1 to C6 alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, C2 to C18 alkenyl or alkynyl, C7 to C18 aralkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C18 arylene, C7 to C18 aralkylene;
R2 is selected from hydrogen, chlorine, bromine, -OH, C1 to C18 straight or branched chain alkyl, C5 to C18 cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II), a group wherein R11, R12 are selected from hydrogen or C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aralkyl;
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) ruling the condition that at least one of the radicals -X-R1-Y- and -(Z) -R2 contains a piperidine radical of formula (II), effective to increase the light stability of said synthetic polymer.
29. A compound having the formula (I):
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from lower alkyl, and R6 is selected from H, C1 to C18 straight or branched chain alkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C10 arylene, C7 to C10 aralkylene;
R2 is selected from hydrogen, chlorine, C1 to C18 straight or branched chain alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II), m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
or where -XR1-Y- represent a radical selected from , , or where -X-R1-Y- represent a residue in which R9 and R10 are hydrogen, C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, or C7 to C12 aralkyl;
with the proviso that at least one of the radicals -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II).
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from lower alkyl, and R6 is selected from H, C1 to C18 straight or branched chain alkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C10 arylene, C7 to C10 aralkylene;
R2 is selected from hydrogen, chlorine, C1 to C18 straight or branched chain alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II), m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
or where -XR1-Y- represent a radical selected from , , or where -X-R1-Y- represent a residue in which R9 and R10 are hydrogen, C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, or C7 to C12 aralkyl;
with the proviso that at least one of the radicals -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II).
30. A compound according to claim 29 having the formula (I):
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from lower alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C10 arylene, C7 to C10 aralkylene;
R2 is selected from hydrogen, chlorine, C1 to C18 straight or branched chain alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II);
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) the condition there is that at least one of the radicals -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II).
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from lower alkyl, and R6 is selected from H, O, C1 to C18 straight or branched chain alkyl, R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C10 arylene, C7 to C10 aralkylene;
R2 is selected from hydrogen, chlorine, C1 to C18 straight or branched chain alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II);
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) the condition there is that at least one of the radicals -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II).
31. A compound according to claim 30, wherein -X-R1-Y-represents a radical selected from , ,
32. A compound according to claim 30 wherein the group -X-R1-Y- represents a residue in which R9 and R10, the same or different are members selected from hydrogen, C1 to C12 alkyl, C5 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aralkyl.
33. A compound according to claim 30 wherein m is one and the radical R2-Z- is the same as -X-R1-YH.
34. A compound according to claim 30 wherein R3 is select-ed from hydrogen, C1 to C12 straight or branched chain alkyl, and a piperidine radical of formula (II).
35. A compound according to claim 30 wherein R1 is select-ed from straight or branched chain C2 to C10, alkylene, and C6 to C10 arylene.
36. A compound according to claim 30 wherein R2 is select-ed from hydrogen, a C1 to C12 straight or branched chain alkyl, and a piperidine radical of formula (II).
37. A compound according to claim 30 wherein the radical R2-Z- is Pip being the radical of formula (II).
38. A compound according to claim 30 wherein A is hydrogen and B is -X-R1-YH.
39. A compound according to claim 37 wherein A is hydrogen and B is
40. A compound according to claim 30, wherein R4, R5, R7, R8 are each methyl and R6 is hydrogen or methyl.
41. A compound according to claim 30, wherein R1 is C2 to C10 alkylene or C6 to C8 arylene;
R2 is H, C4 to C12 alkyl or piperidyl of formula (II);
R3 is H, C4 to C12 alkyl or piperidyl of formula (II);
R4, R5, R7 and R8 are methyl;
R6 is hydrogen or methyl;
R9, R10, R11, R12 are hydrogen;
X, Y, Z represents -O-, -NH-, or Pip being a piperidyl of formula (II);
A is H;
B is r being an integer from 2 to 6;
m is 0 or 1; and n is an integer from 2 to 100.
R2 is H, C4 to C12 alkyl or piperidyl of formula (II);
R3 is H, C4 to C12 alkyl or piperidyl of formula (II);
R4, R5, R7 and R8 are methyl;
R6 is hydrogen or methyl;
R9, R10, R11, R12 are hydrogen;
X, Y, Z represents -O-, -NH-, or Pip being a piperidyl of formula (II);
A is H;
B is r being an integer from 2 to 6;
m is 0 or 1; and n is an integer from 2 to 100.
42. A synthetic polymer of increased stability having in-corporated with the polymer an amount of a compound according to claim 29 effective to increase the light stability of the polymer.
43. A composition according to claim 42 wherein -XR1-Y-represent a bivalent heterocyclic group having 6 to 8 nitrogen atoms with X and Y each representing a disubstituted nitrogen atom or where -X-R1-Y- represent a residue
44. A composition according to claim 42, wherein said synthetic polymer is a polyolefin.
45. A composition according to claim 44, wherein said synthetic polymer is polypropylene.
46. A composition according to claim 44, wherein said synthetic polymer is polyethylene.
47. A composition according to claim 44, wherein said synthetic polymer is in the form of fibers or film.
48. A composition according to claim 42, wherein said compound is added to the synthetic polymer composition in an amount from 0.1 to 1% by weight referred to the synthetic polymer composition.
49. A synthetic polymer of increased stability having incorporated with the polymer an amount of a compound according to claim 30 effective to increase the light stability of the polymer.
50. A method of producing a compound having the general formula (I):
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8 9 the same or different, are members selected from lower alkyl, and R6 is selected from H, C1 to C18 straight or branched chain alkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C10 arylene, C7 to C10 aralkylene;
R2 is selected from hydrogen, chlorine, C1 to C18 straight or branched chain alkyl, C5 to C18 and (b) cyanuric halide in solution in inert solvent, at a temperature from -10°C to the solvent boiling temperature, in the presence of an organic or in-organic base.
(I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8 9 the same or different, are members selected from lower alkyl, and R6 is selected from H, C1 to C18 straight or branched chain alkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C10 arylene, C7 to C10 aralkylene;
R2 is selected from hydrogen, chlorine, C1 to C18 straight or branched chain alkyl, C5 to C18 and (b) cyanuric halide in solution in inert solvent, at a temperature from -10°C to the solvent boiling temperature, in the presence of an organic or in-organic base.
51. The method according to claim 50, comprising reacting 2,4-dihalogentriazines of formula (III) with a compound of formula (IV) in a molar ratio from 1:1.5 to 1.5:1 .
52. A method according to claim 50, in which said halogen is chlorine.
53. A method according to claim 50, comprising reacting a cyanuric halide with a compound of formula (IV) in a molar ratio from 1:1 to 1:1.2, to obtain a product having the formula (VI) (VI) (VI) in which m is as defined in formula (I) is zero.
54. A method according to claim 53, wherein said product (VI) is successively reacted with a compound of formula (V) to obtain a product of formula (I) in which m is 1.
55. A method according to claim 50, comprising reacting a cyanuric halide with a compound of formula (IV) in a molar ratio from 1:2.4 to 1:2.1 to obtain a product of formula (VII) )VII) (VII)
56. A method of increasing the light stability of a synthetic polymer, comprising adding to a composition of material of said synthetic polymer, an amount of a compound having the formula (I):
cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II);
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) there is the condition that at least one of the radical -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II), comprising reacting a compound of formula (IV):
HX - R1 - YH (IV) X, Y, R1 having the meaning as previously defined, with a member of the group consisting of a) 2,4-dihalogentriazines of formula (III) (III) (I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from lower alkyl, and R6 is selected from H, C1 to C18 straight or branched chain alkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C10 arylene, C7 to C10 aralkylene;
R2 is selected from hydrogen, chlorine, C1 to C18 straight or branched chain alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II);
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) ruling the condition that at least one of the radicals -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II), effective to increase the light stability of said synthetic polymer.
cycloalkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II);
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) there is the condition that at least one of the radical -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II), comprising reacting a compound of formula (IV):
HX - R1 - YH (IV) X, Y, R1 having the meaning as previously defined, with a member of the group consisting of a) 2,4-dihalogentriazines of formula (III) (III) (I) wherein X, Y, Z, the same or different, is a member selected from -O-, -S-, R3 being a member selected from hydrogen, straight or branched chain C1 to C18 alkyl, C5 to C18 cyclo-alkyl, a piperidine radical of formula (II):
(II) wherein R4, R5, R7, R8, the same or different, are members selected from lower alkyl, and R6 is selected from H, C1 to C18 straight or branched chain alkyl;
R1 is selected from C2 to C18 straight or branched chain alkylene, C5 to C18 cycloalkylene, C6 to C10 arylene, C7 to C10 aralkylene;
R2 is selected from hydrogen, chlorine, C1 to C18 straight or branched chain alkyl, C5 to C18 cyclo-alkyl, substituted or not substituted C6 to C18 aryl, C7 to C18 aralkyl, a piperidine radical of formula (II);
m is an integer from 0 to 1;
n is an integer from 2 to 200;
A, B are the terminal groups, A being H or and B is halogen or -X-R1-YH;
in formula (I) ruling the condition that at least one of the radicals -X-R1-Y- and -(Z)m-R2 contains a piperidine radical of formula (II), effective to increase the light stability of said synthetic polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT52527/75A IT1052501B (en) | 1975-12-04 | 1975-12-04 | POLYTHRIAZIN COMPOUNDS USABLE FOR THE STABILIZATION OF SYNTHETIC POLYMERS AND PROCEDURE FOR THEIR PREPARATION |
| IT52527A75 | 1975-12-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1085835A true CA1085835A (en) | 1980-09-16 |
Family
ID=11277205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA255,636A Expired CA1085835A (en) | 1975-12-04 | 1976-06-24 | Polytriazine compounds |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US4086204A (en) |
| JP (1) | JPS5271486A (en) |
| AT (1) | AT350276B (en) |
| AU (1) | AU504244B2 (en) |
| BE (1) | BE847239A (en) |
| CA (1) | CA1085835A (en) |
| DE (1) | DE2636144C3 (en) |
| DK (1) | DK167016B1 (en) |
| ES (1) | ES453955A1 (en) |
| FR (1) | FR2333821A1 (en) |
| GB (1) | GB1496635A (en) |
| HK (1) | HK23879A (en) |
| IE (1) | IE43013B1 (en) |
| IT (1) | IT1052501B (en) |
| LU (1) | LU75879A1 (en) |
| NL (1) | NL167429C (en) |
| SU (1) | SU686628A3 (en) |
| ZA (1) | ZA767186B (en) |
Families Citing this family (150)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4161592A (en) * | 1976-07-08 | 1979-07-17 | Ciba-Geigy Corporation | Piperidinyl-s-triazines |
| US4256627A (en) * | 1977-11-08 | 1981-03-17 | Ciba-Geigy Corporation | Novel light stabilizers for plastics |
| US4234707A (en) * | 1977-11-10 | 1980-11-18 | Ciba-Geigy Corporation | Polymeric light stabilizers for plastics |
| EP0002754B1 (en) * | 1977-12-30 | 1983-05-18 | Ciba-Geigy Ag | New polyalkylpiperidine derivatives of s-triazines, their use in the stabilisation of plastics and plastics stabilized in this way |
| 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 |
| DE2963604D1 (en) * | 1978-06-21 | 1982-10-28 | Ciba Geigy Ag | Light stabilization of acid catalysed stoving enamels |
| JPS554331A (en) * | 1978-06-24 | 1980-01-12 | Sankyo Co Ltd | Piperidine-spiro-hydantoin derivative |
| US4315859A (en) * | 1979-01-15 | 1982-02-16 | Ciba-Geigy Corporation | 1,3,5-Triazines containing at least one piperidine radical |
| 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 |
| US4288593A (en) * | 1979-02-06 | 1981-09-08 | Ciba-Geigy Corporation | Polyalkylpiperidine derivatives of s-triazines |
| US4297492A (en) * | 1979-03-23 | 1981-10-27 | Ciba-Geigy Corporation | Phenolic-1,3,5-triazines |
| JPS564639A (en) * | 1979-06-23 | 1981-01-19 | Sankyo Co Ltd | Stabilizer for high-molecular material |
| 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 |
| US4370443A (en) * | 1980-03-03 | 1983-01-25 | Sterling Drug Inc. | Novel polymeric compounds, processes and methods of use |
| US4347352A (en) * | 1980-03-03 | 1982-08-31 | Sterling Drug Inc. | Novel polymeric compounds, processes and methods of use |
| US4314001A (en) * | 1980-03-03 | 1982-02-02 | Sterling Drug Inc. | Novel polymeric compounds, processes and methods of use |
| DE3022453A1 (en) * | 1980-06-14 | 1982-01-07 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING MICROCAPSULES |
| 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 |
| IT1151035B (en) * | 1980-07-31 | 1986-12-17 | Chimosa Chimica Organica Spa | PIPERIDYL-DERIVATIVES OF TRIAZINIC COPOLYMERS, PROCESSES FOR THEIR PREPARATION AND STABILIZED COMPOSITIONS THAT INCLUDE THEM |
| DE3045839A1 (en) * | 1980-12-05 | 1982-07-08 | Hoechst Ag, 6000 Frankfurt | POLY-BIS-TRIAZINYLAMINE, METHOD FOR THE PRODUCTION THEREOF, THEIR USE FOR STABILIZING SYNTHETIC POLYMERS AND THE STABILIZED POLYMERS |
| DE3111209A1 (en) * | 1981-03-21 | 1982-09-30 | Hoechst Ag, 6000 Frankfurt | HIGH MOLECULAR PIPERIDING GROUP-CONTAINING ESTERS AND URETHANES, METHOD FOR THE PRODUCTION THEREOF, THEIR USE AS STABILIZERS FOR POLYMERS AND POLYMERS CONTAINING THESE COMPOUNDS |
| 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 |
| US4616051A (en) * | 1981-05-04 | 1986-10-07 | Uniroyal Chemical Company, Inc. | Combination of phenolic antioxidant and stabilizer for use in organic material |
| DE3117964A1 (en) * | 1981-05-07 | 1982-11-25 | Hoechst Ag, 6000 Frankfurt | POLY-BIS-TRIAZINYLAMINOTRIAZINYLAMINE, THEIR PRODUCTION, THEIR USE AS LIGHT PROTECTION AGENTS FOR PLASTICS AND PLASTICS STABILIZED WITH THEM |
| DE3118962A1 (en) * | 1981-05-13 | 1982-12-09 | Hoechst Ag, 6000 Frankfurt | PHIPHAZENE SUBSTITUTED BY PIPERIDYL GROUPS, METHODS FOR THE PRODUCTION THEREOF, THEIR USE AS STABILIZERS AND THE POLYMER MATERIALS STABILIZED WITH THEM |
| US4386177A (en) * | 1981-07-20 | 1983-05-31 | American Cyanamid Company | Light stabilizers for polymers containing hindered piperidinyl-substituted 1,3,5 triazine groups |
| US4435555A (en) | 1981-07-20 | 1984-03-06 | American Cyanamid Company | Novel polymeric light stabilizers for polymers |
| US4331586A (en) * | 1981-07-20 | 1982-05-25 | American Cyanamid Company | Novel light stabilizers for polymers |
| US4413093A (en) * | 1981-07-20 | 1983-11-01 | American Cyanamid Company | Method of stabilizing a polymer from degradation by UV radiation |
| US4400505A (en) * | 1981-07-20 | 1983-08-23 | American Cyanamid Company | Triazinyl-piperidines as light stabilizers for polymers |
| 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 |
| EP0080431B1 (en) * | 1981-10-16 | 1986-09-24 | Ciba-Geigy Ag | Synergistic mixture of low and high molecular weight polyalkyl piperidines |
| DE3143920A1 (en) * | 1981-11-05 | 1983-05-11 | Degussa Ag, 6000 Frankfurt | NEW BISMELAMINE |
| JPS5892660A (en) * | 1981-11-27 | 1983-06-02 | Adeka Argus Chem Co Ltd | Piperidylamine compound |
| DE3374449D1 (en) * | 1982-01-29 | 1987-12-17 | Wiggins Teape Group Ltd | Photographic base papers |
| US4480092A (en) * | 1982-02-19 | 1984-10-30 | The B. F. Goodrich Company | Alkylated polyalkylenepolyamines, substituted oxo-piperazinyl-triazines |
| US4562246A (en) * | 1982-04-08 | 1985-12-31 | American Cyanamid Company | Essentially linear, thermoplastic poly (amino-s-triazines)s and process for the production thereof |
| JPS58179240A (en) * | 1982-04-15 | 1983-10-20 | Mitsubishi Petrochem Co Ltd | Surface treatment of moldings |
| US4492791A (en) * | 1982-05-04 | 1985-01-08 | Ciba-Geigy Corporation | Process for the preparation of polyaminotriazines |
| IT1152192B (en) * | 1982-05-19 | 1986-12-31 | Apital Prod Ind | COMPOUNDS FOR STABILIZING POLYMERS |
| DE3379050D1 (en) * | 1982-08-11 | 1989-03-02 | Ciba Geigy Ag | Process for the chemical bond between a stabilising compound and a polymer |
| CA1242918A (en) * | 1982-11-18 | 1988-10-11 | David G. Leppart | Colour-photographic recording material |
| JPS59126439A (en) * | 1983-01-10 | 1984-07-21 | Adeka Argus Chem Co Ltd | Stabilized high polymer material composition |
| IT1164214B (en) * | 1983-05-09 | 1987-04-08 | Chimosa Chimica Organica Spa | POLYMERIC COMPOUNDS CONTAINING PIPERIDINIC RADICALS, PROCESS FOR THEIR PREPARATION AND USE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| IT1163814B (en) * | 1983-07-19 | 1987-04-08 | Chimosa Chimica Organica Spa | POLYMERIC COMPOUNDS CONTAINING PIPERIDINIC AND TRIAZINIC RADICALS, PROCESS FOR THEIR PREPARATION AND USE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| IT1163815B (en) * | 1983-07-19 | 1987-04-08 | Chimosa Chimica Organica Spa | POLYMERIC COMPOUNDS CONTAINING PIPERIDINIC RADICALS PROCESS FOR THEIR PREPARATION AND USE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| IT1169843B (en) * | 1983-09-23 | 1987-06-03 | Chimosa Chimica Organica Spa | POLYMERIC COMPOUNDS CONTAINING PIPERIDINIC RADICALS, PROCESS FOR THEIR PREPARATION AND USE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| US4696959A (en) * | 1983-09-26 | 1987-09-29 | Ppg Industries, Inc. | Modified piperidines as ultraviolet light stabilizers |
| JPS60188958A (en) * | 1984-03-08 | 1985-09-26 | Sumitomo Chem Co Ltd | Electrostatic charge image developing toner |
| US4965301A (en) * | 1984-12-03 | 1990-10-23 | Phillips Petroleum Company | Stabilization of polyolefins |
| JPS6218444A (en) * | 1985-07-16 | 1987-01-27 | Adeka Argus Chem Co Ltd | Stabilized polymeric material composition |
| US4629752A (en) | 1985-07-22 | 1986-12-16 | The B. F. Goodrich Company | Substituted oxo-piperazinyl-triazines and UV light stabilized compositions |
| JPS6250342A (en) * | 1985-08-30 | 1987-03-05 | Adeka Argus Chem Co Ltd | Stabilized high-molecular material composition |
| US4762872A (en) * | 1985-11-01 | 1988-08-09 | The B. F. Goodrich Company | Oligomeric light stabilizers with substituted piperidine ends |
| US4746692A (en) * | 1986-05-05 | 1988-05-24 | Shell Oil Company | Polyolefin compositions for use with water systems |
| IT1204389B (en) * | 1986-06-16 | 1989-03-01 | Ciba Geigy Spa | TRIAZINIC DERIVATIVES OF PIPERIDYLYAMIDINS SUITABLE FOR USE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| US4863981A (en) * | 1986-06-30 | 1989-09-05 | Ciba-Geigy Corporation | Synergistic mixture of stabilizers |
| IT1197853B (en) * | 1986-08-07 | 1988-12-21 | Ciba Geigy Spa | POLYTHRIAZIN COMPOUNDS CONTAINING PIPERIDYLYAMIDIN GROUPS AND THEIR USE AS POLYMER STABILIZERS |
| US4985479A (en) * | 1986-11-27 | 1991-01-15 | Sumitomo Chemical Company, Ltd. | Stabilized polyolefin composition |
| IT1215455B (en) * | 1987-05-05 | 1990-02-14 | Ciba Geigy Spa | STABILIZING COMPOSITION FOR POLYETHYLENE INCLUDING COMPOUNDS CONTAINING PIPERIDINIC GROUPS AND METALLIC COMPOUNDS |
| US4751073A (en) * | 1987-06-03 | 1988-06-14 | Olin Corporation | Selected 2,2,6,6-tetraalkyl-4-piperidinyl derivatives and their use as light stabilizers |
| US4812500A (en) * | 1987-09-30 | 1989-03-14 | Shell Oil Company | Polyolefin compositions for water pipes and for wire and cable coatings |
| NL8702473A (en) * | 1987-10-16 | 1989-05-16 | Gen Electric | POLYMER MIXTURE WITH POLYPHENYLENE ETHER, STERICALLY Hindered AMINE AND EPOXY COMPOUND AND ARTICLES THEREFOR. |
| US5210119A (en) * | 1987-10-16 | 1993-05-11 | General Electric Company | Polymer mixture comprising polyphenylene ether, sterically hindered amine and epoxy compound and articles manufactured therefrom |
| IT1223405B (en) * | 1987-12-04 | 1990-09-19 | Ciba Geigy Spa | PROCEDURE FOR THE METHYLATION OF TRIAZINIC COMPOUNDS CONTAINING GROUPS 2,2,6,6 TETRAMETHYLPIPERIDINIC |
| AU621082B2 (en) * | 1988-02-08 | 1992-03-05 | Ciba-Geigy Ag | Tetramethylpiperidino-s-triazines |
| US4968736A (en) * | 1988-02-29 | 1990-11-06 | Willcox Kenneth W | Corrosion inhibition of polymethylpentene |
| US4793972A (en) * | 1988-02-29 | 1988-12-27 | Phillips Petroleum Company | Corrosion inhibition of polymethylpentene |
| US5066460A (en) * | 1988-02-29 | 1991-11-19 | Phillips Petroleum Company | Corrosion inhibition of polymethylpentene |
| US5000917A (en) * | 1988-02-29 | 1991-03-19 | Phillips Petroleum Company | Corrosion inhibition of polymethylphenthene |
| CS270846B1 (en) * | 1988-08-29 | 1990-08-14 | Vass Frantisek | New polyaminotriazines and method of their preparation |
| US4981964A (en) * | 1988-12-15 | 1991-01-01 | Ici Americas Inc. | Oligomeric polyesters and polyamides containing dipiperidyl triazine groups |
| DE3932912A1 (en) * | 1989-10-03 | 1991-04-11 | Sandoz Ag | Synthetic polyamide(s) for plastics, inks and lacquers |
| EP0461206B1 (en) * | 1989-09-09 | 1994-03-02 | Sandoz-Patent-Gmbh | Synthetic polyamides and their salts |
| IT1237129B (en) * | 1989-11-10 | 1993-05-18 | Valerio Borzatta | PIPERIDIN TRIAZINIC COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS. |
| IT1237541B (en) * | 1989-12-28 | 1993-06-08 | Ciba Geigy | PIPERIDIN TRIAZIN COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS |
| US5066696A (en) * | 1990-02-12 | 1991-11-19 | Rohm And Haas Company | Polymers stabilized against light and heat degradation |
| IT1248698B (en) * | 1990-06-06 | 1995-01-26 | Ciba Geigy Spa | PIEPRIDIN TRIAZIN COMPOUNDS CONTAINING SILOXANE GROUPS, SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS |
| US5324834A (en) * | 1990-06-13 | 1994-06-28 | Ciba-Geigy Corporation | Piperidine-triazine co-oligomers for use as stabilizers for organic materials |
| JP2903739B2 (en) * | 1990-06-29 | 1999-06-14 | 住友化学工業株式会社 | Method for producing N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) alkanediamine |
| IT1246170B (en) * | 1990-07-24 | 1994-11-16 | Ciba Geigy Spa | POLYPROPYLENE STABILIZING COMPOSITION INCLUDING TRIAZINIC COMPOUNDS CONTAINING PIPERIDINIC GROUPS AND METALLIC COMPOUNDS |
| IT1243374B (en) * | 1990-07-27 | 1994-06-10 | Ciba Geigy Spa | PIPERIDIN TRIAZIN COMPOUNDS CONTAINING TETRAIDROFURANIC OR TETRAIDROPYRANIC GROUPS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS |
| IT1243433B (en) * | 1990-10-03 | 1994-06-10 | Ciba Geigy Spa | PIPERIDIN TRIAZIN COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS |
| US5256787A (en) * | 1990-09-03 | 1993-10-26 | Ciba-Geigy Corporation | Tri-piperdine compounds as stabilizers for organic materials |
| JP2520984B2 (en) * | 1991-02-27 | 1996-07-31 | 三菱化学エムケーブイ株式会社 | Polyolefin resin film for agriculture |
| US5149723A (en) * | 1991-03-22 | 1992-09-22 | E. I. Du Pont De Nemours And Company | Stabilized polyacetal compositions containing a mixture of hals having tertiary functionality |
| JPH05156094A (en) * | 1991-12-11 | 1993-06-22 | Sumitomo Chem Co Ltd | Stabilized polyolefin composition |
| IT1254689B (en) * | 1992-04-14 | 1995-09-28 | PIPERIDIN-TRIAZINIC COOLIGOMERS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS. | |
| ES2115744T3 (en) * | 1992-05-13 | 1998-07-01 | Ciba Geigy Ag | STABILIZED COMPOSITIONS OF CHLORINE POLYMERS. |
| EP0604823A1 (en) * | 1992-12-29 | 1994-07-06 | International Business Machines Corporation | Triazine polymer and use thereof |
| IT1263892B (en) * | 1993-02-11 | 1996-09-05 | Graziano Vignali | PIPERIDIN-TRIAZIN COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS |
| GB2279649B (en) * | 1993-07-08 | 1997-07-16 | Ciba Geigy Ag | Phenolic s-triazines |
| TW302377B (en) | 1993-12-24 | 1997-04-11 | Sumitomo Chemical Co | |
| FR2717809B1 (en) * | 1994-03-24 | 1997-09-19 | Sandoz Sa | S-triazine derivatives, their preparation and their use as UV absorbers. |
| EP0709426B2 (en) | 1994-10-28 | 2005-01-05 | Ciba SC Holding AG | Synergistic stabiliser mixture |
| DE59508533D1 (en) * | 1994-10-28 | 2000-08-10 | Ciba Sc Holding Ag | Synergistic stabilizer mixture |
| TW401437B (en) * | 1995-02-10 | 2000-08-11 | Ciba Sc Holding Ag | Synergistic stabilizer mixture |
| TW358820B (en) | 1995-04-11 | 1999-05-21 | Ciba Sc Holding Ag | Synergistic stabilizer mixture |
| TW360678B (en) * | 1995-05-03 | 1999-06-11 | Ciba Sc Holding Ag | Synergistic stabilizer mixture for polyolefins |
| US5603885A (en) * | 1995-07-06 | 1997-02-18 | E. I. Du Pont De Nemours And Company | Process for the preparation of nonwoven fibrous sheets |
| TW390897B (en) * | 1995-07-21 | 2000-05-21 | Ciba Sc Holding Ag | Synergistic stabilizer mixture |
| IT1275584B1 (en) * | 1995-07-21 | 1997-08-06 | 3V Sigma Spa | COMPOSITIONS FOR THE STABILIZATION OF SYNTHETIC POLYMERS |
| US6046304A (en) | 1995-12-04 | 2000-04-04 | Ciba Specialty Chemicals Corporation | Block oligomers containing 2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials |
| EP0782994B1 (en) * | 1995-12-04 | 2003-02-05 | Ciba SC Holding AG | Block oligomers containing 2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials |
| ES2128978B1 (en) * | 1996-04-01 | 2000-03-01 | Ciba Sc Holding Ag | POLYTHRIAZINE DERIVATIVES CONTAINING GROUPS OF POLYALKYLPIPERIDINYLOXYL OR POLYALKYLPIPERIDINYLAMINE. |
| KR980009326A (en) * | 1996-07-09 | 1998-04-30 | 고사이 아키오 | Polyaminotriazines, Preparation Methods thereof and Uses thereof |
| EP0819730B1 (en) * | 1996-07-17 | 2005-04-06 | Ciba SC Holding AG | Ozone resistant long-time stabilisers |
| DE69719004T2 (en) | 1996-12-24 | 2003-07-24 | Ciba Sc Holding Ag | Triazine compounds containing 2,2,6,6-tetramethyl-4-piperidine groups as stabilizers for organic materials |
| TW491872B (en) * | 1997-05-27 | 2002-06-21 | Ciba Sc Holding Ag | Block oligomers containing l-hydrocarbyloxy-2,2,6,6-tetramethyl-4- piperidyl groups as stabilizers for lower polyolefin |
| TW509683B (en) * | 1997-05-27 | 2002-11-11 | Ciba Sc Holding Ag | Triazine derivatives containing 2,2,6,6-tetramethyl-4-piperidyl groups |
| US6403680B1 (en) | 1997-05-27 | 2002-06-11 | Ciba Specialty Chemicals Corporation | Block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials |
| TW589341B (en) | 1997-05-27 | 2004-06-01 | Ciba Sc Holding Ag | Block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials |
| TW428008B (en) | 1997-05-27 | 2001-04-01 | Ciba Sc Holding Ag | Block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethy1-4-piperidyl groups as stabilizers for organic materials |
| KR100533909B1 (en) | 1997-05-27 | 2005-12-07 | 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 | Block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials |
| IT1292040B1 (en) * | 1997-05-30 | 1999-01-25 | Ciba Spec Chem Spa | PROCESS FOR THE PREPARATION OF POLYTRIAZINE PRODUCTS CONTAINING 2,2,6,6-TETRAMETHYL-4-PIPERIDYL GROUPS |
| WO1999029684A1 (en) * | 1997-12-08 | 1999-06-17 | Cytec Technology Corp. | Morpholino end-capped, hindered amine substituted aminotriazine and their use as light stabilizers |
| KR100786241B1 (en) * | 2000-05-31 | 2007-12-17 | 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 | Stabilizer mixtures |
| US6433088B1 (en) | 2000-08-04 | 2002-08-13 | Equistar Chemicals, Lp | Clear and printable polypropylene films |
| US6514626B1 (en) * | 2000-08-28 | 2003-02-04 | Pechiney Emballage Flexible Europe | Dienophile additives to polyvinylidene chloride copolymers |
| US6355733B1 (en) | 2000-10-13 | 2002-03-12 | Equistar Chemicals, Lp | Polyethylene blends and films |
| US6747077B2 (en) | 2000-10-17 | 2004-06-08 | Ciba Specialty Chemicals Corporation | Stabilized metallocene polypropylene |
| US6414155B1 (en) | 2000-11-03 | 2002-07-02 | Cytec Technology Corp. | Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same |
| US6545156B1 (en) | 2000-11-03 | 2003-04-08 | Cytec Technology Corp. | Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same |
| US6492521B2 (en) | 2000-11-03 | 2002-12-10 | Cytec Technology Corp. | Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same |
| US6727300B2 (en) | 2000-11-03 | 2004-04-27 | Cytec Technology Corp. | Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds |
| US6465645B1 (en) | 2001-04-17 | 2002-10-15 | Ciba Specialty Chemicals Corporation | Long chain hindered amines and compositions stabilized therewith |
| US6613841B2 (en) | 2002-01-28 | 2003-09-02 | Equistar Chemicals, Lp | Preparation of machine direction oriented polyethylene films |
| US20030225191A1 (en) | 2002-04-12 | 2003-12-04 | Francois Gugumus | Stabilizer mixtures |
| US6649698B1 (en) | 2002-05-17 | 2003-11-18 | Equistar Chemicals, Lp | Polyethylene blends |
| US20030236325A1 (en) * | 2002-05-30 | 2003-12-25 | Michela Bonora | Agricultural articles |
| ES2301819T3 (en) * | 2002-05-30 | 2008-07-01 | Ciba Specialty Chemicals Holding Inc. | STABILIZED ITEMS. |
| US6903162B2 (en) * | 2003-07-01 | 2005-06-07 | Equistar Chemicals, Lp | Preparation of polyethylene films |
| US7175918B2 (en) * | 2004-04-27 | 2007-02-13 | Equistar Chemicals, Lp | Polyolefin compositions |
| US7608327B2 (en) * | 2005-12-20 | 2009-10-27 | Equistar Chemicals, Lp | High tear strength film |
| CN101541870A (en) * | 2006-11-27 | 2009-09-23 | 西巴控股有限公司 | Bitumen or asphalt compositions stabilised against weathering |
| ITMI20080739A1 (en) | 2008-04-23 | 2009-10-24 | 3V Sigma Spa | STERICALLY PREVENTED OLIGOMERIC STAKES AND THEIR USE AS STABILIZERS FOR POLYMERS |
| ITMI20080747A1 (en) * | 2008-04-24 | 2009-10-25 | 3V Sigma Spa | MIXTURES OF STERICALLY PREVENTED AMINES FOR THE STABILIZATION OF POLYMERS |
| EP2130854B1 (en) | 2008-05-09 | 2016-10-19 | MCA Technologies GMBH | Polytriazinyl compounds as flame retardants and light stabilizers |
| IT1393333B1 (en) | 2009-02-09 | 2012-04-20 | 3V Sigma Spa | NEW STERICALLY PREVENTED FINES AND THEIR USE AS STABILIZERS FOR POLYMERS |
| EP2467878A1 (en) | 2009-08-18 | 2012-06-27 | Basf Se | An uv-stabilized photovoltaic module |
| US20110045265A1 (en) | 2009-08-20 | 2011-02-24 | Haley Jeffrey C | Polyolefin composition and film thereof |
| IT1399477B1 (en) | 2010-03-15 | 2013-04-19 | 3V Sigma Spa | MIXTURES OF STERICALLY PREVENTED AMINES FOR THE STABILIZATION OF POLYMERS |
| US8637607B2 (en) | 2010-07-28 | 2014-01-28 | Equistar Chemicals, Lp | Polyethylene blends and films |
| IT1403086B1 (en) | 2010-10-28 | 2013-10-04 | 3V Sigma Spa | NEW STERICALLY PREVENTED POLYMERIC AMINES AND THEIR USE AS STABILIZERS FOR POLYMERS |
| ITMI20110802A1 (en) | 2011-05-10 | 2012-11-11 | 3V Sigma Spa | MIXTURES OF STERICALLY PREVENTED AMINES FOR THE STABILIZATION OF POLYMERS |
| SA116370295B1 (en) | 2015-02-20 | 2016-12-06 | باسف اس اى | Light stabilized polyolefin films, tapes and monofilaments |
| IT201700073726A1 (en) | 2017-06-30 | 2018-12-30 | 3V Sigma Spa | IMPEDITE POLYMERIC AMINS |
| IT201700078234A1 (en) | 2017-07-11 | 2019-01-11 | 3V Sigma Spa | IMPEDINE MINES |
| EP4301731A1 (en) | 2021-03-05 | 2024-01-10 | Basf Se | Process for preparing n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2640047A (en) * | 1951-05-10 | 1953-05-26 | American Cyanamid Co | Reaction products of a polyhalogenated compound and a triazine derivative and methods of preparing the same |
| GB930674A (en) * | 1960-03-22 | 1963-07-10 | Artrite Resins Ltd | Polymeric compounds containing s-triazine nuclei |
| US3297639A (en) * | 1963-02-05 | 1967-01-10 | Lewellyn G Picklesimer | Polyethers of triazine and polyhydric aromatic compounds |
| US3301797A (en) * | 1964-03-06 | 1967-01-31 | American Cyanamid Co | Linear triazine polymers |
| DE1670529C3 (en) * | 1966-07-13 | 1974-01-10 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Substituted s-triazines |
| US3576805A (en) * | 1969-05-22 | 1971-04-27 | American Cyanamid Co | N**2,n**4,n**6-trisubstituted melamines |
| US3850918A (en) * | 1970-06-17 | 1974-11-26 | Ciba Geigy Corp | 2-amino-4,6-disalicyloyl-hydrazino-s-triazines |
| GB1393551A (en) * | 1972-04-21 | 1975-05-07 | Ciba Geigy Ag | Piperidine derivatives |
| DE2246106C2 (en) * | 1972-09-20 | 1983-02-24 | Bayer Ag, 5090 Leverkusen | High molecular weight polycarbonates containing s-triazine rings |
| DE2360709A1 (en) * | 1973-12-06 | 1975-06-12 | Bayer Ag | S-TRIAZINE PRE-POLYMERIZES |
-
1975
- 1975-12-04 IT IT52527/75A patent/IT1052501B/en active
-
1976
- 1976-06-21 DK DK277576A patent/DK167016B1/en not_active IP Right Cessation
- 1976-06-23 IE IE1368/76A patent/IE43013B1/en unknown
- 1976-06-23 US US05/699,162 patent/US4086204A/en not_active Expired - Lifetime
- 1976-06-24 CA CA255,636A patent/CA1085835A/en not_active Expired
- 1976-06-29 GB GB27099/76A patent/GB1496635A/en not_active Expired
- 1976-07-14 SU SU762382814A patent/SU686628A3/en active
- 1976-07-22 JP JP51086679A patent/JPS5271486A/en active Granted
- 1976-08-11 DE DE2636144A patent/DE2636144C3/en not_active Expired
- 1976-08-26 FR FR7625805A patent/FR2333821A1/en active Granted
- 1976-09-27 LU LU75879A patent/LU75879A1/xx unknown
- 1976-09-27 NL NL7610694.A patent/NL167429C/en not_active IP Right Cessation
- 1976-10-13 BE BE171479A patent/BE847239A/en not_active IP Right Cessation
- 1976-11-26 AU AU20023/76A patent/AU504244B2/en not_active Expired
- 1976-12-02 ZA ZA767186A patent/ZA767186B/en unknown
- 1976-12-03 ES ES453955A patent/ES453955A1/en not_active Expired
- 1976-12-03 AT AT897476A patent/AT350276B/en active
-
1979
- 1979-04-04 HK HK238/79A patent/HK23879A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU504244B2 (en) | 1979-10-04 |
| DE2636144C3 (en) | 1980-07-10 |
| ATA897476A (en) | 1978-10-15 |
| JPS5271486A (en) | 1977-06-14 |
| HK23879A (en) | 1979-04-12 |
| FR2333821A1 (en) | 1977-07-01 |
| FR2333821B1 (en) | 1978-05-05 |
| NL167429B (en) | 1981-07-16 |
| JPS5742087B2 (en) | 1982-09-07 |
| ZA767186B (en) | 1977-11-30 |
| NL167429C (en) | 1981-12-16 |
| NL7610694A (en) | 1977-06-07 |
| DE2636144B2 (en) | 1979-10-31 |
| AU2002376A (en) | 1978-06-01 |
| BE847239A (en) | 1977-01-31 |
| DK277576A (en) | 1977-06-05 |
| IE43013B1 (en) | 1980-12-03 |
| SU686628A3 (en) | 1979-09-15 |
| IT1052501B (en) | 1981-07-20 |
| GB1496635A (en) | 1977-12-30 |
| LU75879A1 (en) | 1977-05-06 |
| DK167016B1 (en) | 1993-08-16 |
| IE43013L (en) | 1977-06-04 |
| DE2636144A1 (en) | 1977-06-08 |
| US4086204A (en) | 1978-04-25 |
| ES453955A1 (en) | 1978-02-01 |
| AT350276B (en) | 1979-05-25 |
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