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GB1580940A - Stabilisers for synthetic polymers and a process for their preparation - Google Patents

Stabilisers for synthetic polymers and a process for their preparation Download PDF

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GB1580940A
GB1580940A GB4726077A GB4726077A GB1580940A GB 1580940 A GB1580940 A GB 1580940A GB 4726077 A GB4726077 A GB 4726077A GB 4726077 A GB4726077 A GB 4726077A GB 1580940 A GB1580940 A GB 1580940A
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

The new compounds of formula I, in which the substitutents R1, R2, X, Y and Z have the meanings given in Claim 1 and n is an integer between 7 and 2000, are prepared by reacting a 4,6-disubstituted 2-halo-1,3,5-triazine with a polyamine. The compounds obtained are employed for stabilising synthetic polymers to light, heat and oxidation. <IMAGE>

Description

(54) STABILISERS FOR SYNTHETIC POLYMERS AND A PROCESS FOR THEIR PREPARATION (71) We, CHIMOSA CHIMICA ORGANICA S.p.A. of Pontecchio Marconi (Bologna)-Italy- Via Pila 6/3 a company organised and existing under the laws of Italy do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to new piperidine derivatives of 1 ,3,5-triazine which may be used for improving the resistance of synthetic polymers to light, heat and oxidation.
Synthetic polymers generally undergo severe deterioration when subjected to sunlight or any other source of ultraviolet light.
To improve the resistance to light of these polymers various stabilisers have been proposed some of which are widely used industrially such as certain benzophenones, benzotriazoles, aromatic salicylates, a-cyano-acrylic esters and organostannic compounds which, although having a certain effectiveness, have not enabled the problem to be completely solved.
Various piperidine derivatives having light stabilising properties for synthetic polymers are also known, but in general these compounds are of limited compatibility with polymers and are easily extracted from polymers by aqueous solutions of surface active agents.
These characteristics make such products useless in situations where the stabilised polymers are used for the preparation of fibres or stretched tapes. Because of the high specific surface of the finished products and the prolonged contact with aqueous solutions of surface active agents during processing, some of the stabiliser is lost and the quantity remaining in the finished fibre is no longer sufficient to give satisfactory resistance to light.
Commonly used light stabilisers such as benzophenone derivatives have a limited light stabilising efficiency for polyolefins when used for thin products such as fibres, stretched tapes and thin films. For such applications stabilisers are required which are more effective in protecting the polymer against the damaging action of ultraviolet light, more resistant to extraction by aqueous solutions of surface active agents and more compatible with such solutions.
The present invention comprises piperidine derivatives of 1 ,3,5-triazine which may be used as light stabilisers for synthetic polymers, which are of high compatibility with polyolefins and possess improved resistance to extraction when in contact with aqueous solutions of surface active agents.
The invention also comprises the preparation of polymer compositions stabilised against photodegradation and thermo-oxidation using said piperidine derivatives. The triazine compounds of the present invention have the following formula:
where: R1, R2, which may be the same or different, represents one atom of hydrogen, a linear or branched alkyl containing 1 to 18 C, a cycloalkyl containing 5 to 18 C, an unsubstituted or substituted aryl containing a total of 6 to 18 C, an aryl alkyl containing a total of 7 to 18 C, or a piperidine radical of formula (II):
in which R3, R4, R6, R7, which may be the same or different, represents an alkyl containing 1 to 6 C and R5 represents H, O, an alkyl of 1-12 C, an alkenyl or alkynyl of 2-12 C; X and Y, which may be the same or different, each represent -0-, -S- or
Rs being H or a linear or branched chain alkyl having 1 to 18 C, a cycloalkyl having 5-18 C, substituted or unsubstituted aryl having 6-18 C, an aryl alkyl having 7-18 C, or a piperidine radical of formula (II).
The radicals Rl-X-, R2-Y- may also represent radicals of nitrogenated heterocyclic compounds of 5-8 terms joined to the triazine ring by one atom of nitrogen of said radical, and n is a whole number between 7 and 2000.
Z represents an n-valent radical obtained by eliminating n atoms of active hydrogen from a linear or branched chain polyamine containing at least 7 primary and/or secondary amino groups, the polyamines containing repeating units of the type:
in which Rg, Rlo and R11 which may be the same or different, each represent a 2-12 C alkylene, a 5-12 C cycloalkylene, a 6-12 C arylene, a 7-12 C arylalkylene or a radical.
R12 iS hydrogen, a 1-12 C linear or branched chain alkyl, a 5-12 C cycloalkyl, a substituted or unsubstituted 6-12 C aryl, or a 7-12 C aryl alkyl, and m is zero or 1.
In formula (I), there must be at least one piperidine radical of formula (II) present in the Rl-X- or R2-Y- radicals.
Examples of R1 and R2, besides H, are methyl, ethyl, isopropyl, n-butyl isobutyl, n-hexyl, n-octyl, n-dodecyl, n-octadecyl, cyclohexyl, 3,3,5- trimethylcyclohexyl, phenyl, o-, m-, p-toluyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, a or P-naphthyl, benzyl, p-methylbenzyl, 2,2,6,6-tetramethyl-4- piperidyl, 1,2,2 ,6,6-pentamethyl -4-piperidyl, 1-allyl-2,2,6,6- tetramethyl-4- piperidyl.
Examples of R3, R4, R6 and R7 are methyl, ethyl, n-propyl, n-butyl, n-hexyl.
Examples of Rg, besides hydrogen, are methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-dodecyl, allyl, and propynyl.
Examples of X and Y are -0-, -S-,
where R8 besides being hydrogen can be methyl, ethyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-dodecyl, n-octadecyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, phenyl, p-toluyl, benzyl, 2,2,6,6- tetramethyl-4- piperidyl, 1,2,2,6,6- pentamethyl-4- piperidyl, 1-ethyl- 2,2,6,6tetramethyl-4- piperidyl, or 1-n-propyl- 2,2,6,6- tetramethyl-4- piperidyl.
The radicals Rl-X-, R2-Y- may also represent radicals of 5 to 8 term nitrogenated heterocyclic compounds such as 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl, 4-methyl-i- piperazinyl, 4-methyl-1- homopiperazinyl.
Examples of R9, Rlo and R11 are ethylene, 1,2-propylene, trimethylene, hexamethylene, 2,2,4-trimethylhexamethylene, 2,4,4-trimethylhexamethylene, decamethylene, 1,4 cyclohexylene, 4,4'-methylene- dicyclohexylene, o-, m-, p-phenylene, o-, m-, p-xylylene, and 2-hydroxy- 1,3-propylene.
Examples of polyamines containing repeating units of types (III), (IV), (V) are those polyethyleneimines obtained by cationic polymerisation of ethyleneimine (Kirk-Othmer Encycl. of Chem. Tech. vol. 17, 406), or those polyamines obtained, for example, by reacting a primary diamine with a dihaloalkane (see for example Belgium patent 614,619 and Japanese patent 10,534/60), a dihalocycloalkane, a dihaloarene, a dihaloalkarene or with epichlorohydrin (see for example British patent 950,852). Examples of polyamines containing repeating units of type (VI) are polyvinylamine (see for example British patent 772,345) and polymers and copolymers of allylamine (see for example U.S.A. patent 3,057,833).
Preferably n lies between 7 and 500.
Preparation The triazine compounds of formula (I) may be prepared by reacting a 4,6 disubsituted 2-halo- 1,3,5-triazine of formula (VII):
R1 halogen (VII) R2 wherein the halogen is preferably chlorine, with polyamines characterised by a repeating unit of the type:
wherein Rg, Rlo, R11 and Rl2 are as defined above.
Preferably, 1 mole of intermediate (VII) is used for each NH or NH2 group in the polyamine. However, it is also possible to use a smaller quantity of reactant. (VII), for example 0.1 to 1 mole for each NH or NH2 group of the polyamines, and also to use an excess of reactant (VII).
The reaction between the halotriazine (VII) and the polyamine is preferably carried out in the presence of an inert solvent such as acetone, dioxane, toluene, or xylene, working generally ai the solvent's boiling point.
The reaction is carried out in the presence of organic and inorganic bases for fixing the liberated halogen acid. These bases include triethylamine, tributylamine, sodium hydrate, carbonate or bicarbonate, or potassium hydrate or carbonate.
The following examples illustrate the invention.
EXAMPLE I A) Preparation of 2-chloro- 4,6-bis-[N(2,2,6,6- tetramethyl-4- piperidyl)-n-butylamino] 1,3,5-triazine 212 g (1 mole, of 2,2,6,6- tetramethyl-4-n- butylaminopiperidine dissolved in 100 ml of acetone. are added to a mixture of 92.25 g (0.5 moles) of cyanuric chloride, 700 ml of acetone and 600 g of ice. The temperature of the mixture is raised to 350C, then 40 g (1 mole) of sodium hydrate dissolved in 400 ml of water are added.
The mixture is stirred for 6 hours at 35-400C. The precipitate obtained is filtered, washed with water and dried over anhydrous Cacti2. After crystallisation from xylol, a white crystalline powder is obtained having a melting point of 83-85"C.
Chlorine = 6.48% (calculated for C29H54ClN7 = 6.62%).
B) Preparation of the poly 2 .4-bis [N(2,2,6,6-tetramethyl- 4-piperidyl)-n-butylamino] - 1,3,5-triazin-6-yl derivative of polyethylenimine of molecular weight 450-750.
198 g (0.37 moles) of 2-chloro- 4,6-bis- [N(2,2,6,6- tetramethyl-4. piperidyl)-n butylamino -1,3,5-triazine,21.5 g of polyethyleneimine of molecular weight 450-750, 14.8 g (0.37 moles of sodium hydrate and 500 ml of xylene are refluxed for 16 hours, with stirring.
After filtration followed by evaporation of the solvent at 1 200C under reduced pressure (12 mm.Hg),. a fragile resinous substance of light yellow colour is obtained. M.P. = 120 135"C, N = 20.58%, Cl = 0.17%. The IR spectrum for the product indicates the disappearance of the primary and secondary amino groups present in the initial polyamine.
EXAMPLE 2 Preparation of the poly 2,4-bis [N(2,2,6,6-tetramethyl- 4-piperidyl)- n butylamino] - 1,3 ,5-triazin-6-yl derivative of polyethyleneimine of molecular weight 1050-1350.
198 g (0.37 moles) of 2-chloro-4,6- bis-[N)2,2,6,6- tetramethyl-4- piperidyl)-n- butylamino]- 1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 1050-1350, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are refluxed for 16 hours, with stirring. After filtering and then evaporating the solvent at 1200C under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 131-143"C, N = 20.71%, Cl = 0.12%. The IR spectrum for the product indicates the disappearance of the primary and secondary amino groups present in the initial polyamine.
EXAMPLE 3 Preparation of the poly 2,4-bis [N-(2,2,6,6-tetramethyl- 4-piperidyl). n-butylamino] -1,3,5-triazin- 6-yl derivative of polyethyleneimine of molecular weight 1650-1950.
198 g (0.37 moles) of 2-chloro-4,6-bis [N-(2,2,6,6-tetramethyl- 4- piperidyl)-n- butylamino] 1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 1650-1950, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are refluxed for 16 hours, with stirring.
After filtering and then evaporating the solvent at 1200C under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 161-175"C, N = 20.38%, C1 = 0.23%. The IR spectrum for the product indicates the disappearance of the primary and secondary amino groups present in the initial polyamine.
EXAMPLE 4 A) Prepration of 2-chloro-4,6-bis [N(2,2,6,6- tetramethyl-4- piperidyl) ethylamino] 1,3,5-triazine.
184 g (1 mole) of 2,2,6,6-tetramethyl- 4- ethylaminopiperidine dissolved in 100 ml of acetone are added to a mixture of 92.25 g (0.5 moles) of cyanuric chloride, 500 ml of acetone and 160 g of ice.
The temperature of the mixture is raised to 35 "C, and then 40 g (1 mole) of sodium hydrate dissolved in 100 ml of water are added.
The mixture is stirred for 6 hours at 35-400C. The precipitate is filtered, washed with water and dried over anhydrous Cacti2. On crystallisation from acetone, a white crystalline powder is obtained which melts at 127-129"C.
Chlorine = 7.36% (calculated for C25H46C1N7 = 7.40to).
B) Preparation . of the poly 2,4-bis[N(2,2,6,6- tetramethyl-4- piperidyl) ethylamino] -1,3,5-triazin-6-yl derivative of polyethyleneimine of molecular weight 450-750.
177.4 g (0.37 moles) of 2-chloro- 4,6-bis [N-(2,2,6,6-tetramethyl-4-piperidyl)-ethylamino] -1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 450-750, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are refluxed for 16 hours with stirring.
After filtering and then evaporating the solvent at 1200 under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 168-179"C; N = 23.07%; Cl = 0.15%. The IR spectrum for the product indicated the disappearance of the primary and secondary amino groups present in the initial polyamine.
EXAMPLE 5 Preparation of the poly 2,4-bis [N(2,2,6,6-tetramethyl- 4-piperidyl) ethylamino]- 1,3,5 triazin-6-yl derivative of polyethyleneimine of molecular weight 1050-1350.
177.4 g (0.37 mole) of 2-chloro-4,6-bis [N-(2,2,6,6-tetramethyl- 4-piperidyl)- ethylamino] 1,3,5-triazine, 21.5 g of polyethyleneimine of molecular weight 1050-1350, 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are refluxed for 16 hours with stirring. After filtering and then evaporating the solvent at 1200C under reduce'd pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 156-167"C; N = 22.95%; Cl = 0.10%. The I.R. spectrum for the product indicates the disappearance of the primary and secondary amino groups present in the initial polyamine.
EXAMPLE 6 A) Preparation of 2-chloro- 4,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)- 1,3,5- triazine, according to the French patent 2,181,059. 18.45 g (0.1 moles) of cyanuric chloride are suspended in 600 ml of water and then 31.2 g (0.2 moles) of 4-amino-2,2,6,6- tetramethylpiperidine and a solution of 8 g (0.2 moles) of sodium hydrate in 20 ml of water are added.
The mixture is stirred for 30 minutes at ambient temperature and is then heated at 900C for 16 hours.
After cooling, the precipitate is separated by filtration, washed and dried under vacuum. A.
white powder is obtained with a melting point of277-278 C.
B) Preparation of the poly [2,4-bis(2,2,6,6-tetramethyl- 4- piperidylamino)-1,3,5- triazin 6-ylderivative of polyethyleneimine of molecular weight 450-750.
139.7 g (0.33 moles) of 2-chloro -4,6-bis (2,2,6,6-tetramethyl -4- piperidylamino)-1,3,5triazine, 19.3 g of polyethyleneimine of molecular weight 450-750, 13.2 g (0.33 moles) of sodium hydrate and 800 ml of xylene are refluxed for 16 hours with stirring.
After filtering and then evaporating the solvent at 1200C under reduced pressure (15 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 172-195 C; N = 25.88%; C1 = 0.25%. The IR spectrum for the product indicates the disappearance of the primary and secondary amino groups present in the initial polyamine.
EXAMPLE 7 A) Preparation of hexamethylenediamine- epichlorohydrin copolymer.
580 g (5 moles) of hexamethylenediamine, 370 g (4 moles) of epichlorohydrin and 2000 ml of isopropanol are refluxed for 10 hours. During the last 8 hours 160 g (4 moles) of sodium hydrate are added in small quantities. After filtering and then evaporating the solvent at 1200C under vacuum 12 mm Hg), a soft waxy substance of light yellow colour is obtained having a molecular weight 800. Total N% = 17.19; primary N% = 3.41 secondary N% = 13.78.
B) Preparation of the poly 2,4-bis[N-2,2,6,6-tetramethyl- 4-piperidyl)-n- butylamino] 1,3,5-triazin-6-yl derivatives of the hexamethylenediamine- epichlorohydrin copolymer of molecular weight 800.
198 g (0.37 moles) of 2-chloro-4,6-bis [N(2,2,6,6-tetramethyl- 4-piperidyl)-n- butylamino] a 1,3,5- triazine, 29.6 g of hexamethylenediamine- epichlorohydrin copolymer prepared as in (A), 14.8 g (0.37 moles) of sodium hydrate and 500 ml of xylene are refluxed for 16 hours with stirring.
After filtering and then evaporating the solvent at 1200C under reduced pressure (12 mm Hg), a fragile resinous substance of light yellow colour is obtained. M.P. = 115-130"C; N = 19.12%; C1 = 0.21%. The IR spectrum for the product indicated the disappearance of the primary and secondary amino groups present in the initial polyamine. Compounds of formula (I) are effective in improving the resistance of synthetic polymers to light, heat and oxidation.
Preferably the polymers are high and low density polyethylene, polypropylene, ethylenepropylene copolymers, ethylene-vinylacetate copolymers, polybutadiene, polyisoprene, polystyrene, butadiene-styrene copolymers, acrylonitrile- butadiene-styrene copolymers, polyethylene terephthalate and unsaturated polyesters.
The compounds of formula (I) may be used with the synthetic polymers in mixtures of various proportions depending on the nature of the polymer, the final use of the polymer and the presence of other additives.-In general, it is appropriate to use between 0.01 and by weight of the compounds of formula (I) relative to the weight of the polymers, and preferably 0.1 to 1%.
The compounds of formula (I) may be incorporated into the polymer materials by various methods such as dry mixing in powder form, wet mixing in the form of a solution or suspension or in the form of a master batch. In such operations, the synthetic polymer may be used in the form of a powder, granules, a solution, a suspension or an emulsion. The polymers stabilised by means of the compounds of formula (I) may be used for preparing objects such as moulded objects, films, stretched tapes, fibres and monofilaments.
Further additives may be used in the polymer material if required such as anti-oxidants, UV absorbers, nickel stabilisers, pigments, fillers, plasticisers, antistatic agents, flame retardants, lubricating agents, corrosion protectors and metal deactivators. Additives which may be used in mixture with the compounds of formula (I) are preferably: phenolic anti-oxidants, such as 2,6-di-tert-butyl-p-cresol, 4,4'- thiobis(3- methyl-6-tertbutylphenol), 1,1,3- tris(2-methyl- 4-hydroxy-5- tert-butylphenyl)- butane, octadecyl 3-(3,5-di-tert-butyl -4-hydroxyphenyl)propionate, pentaerithritol tetrakis (3,5-di-tert-butyl4-hydroxyphenyl) propionate and tris (3,5-di-tert- butyl-4- hydroxybenzyl) isocyanate; thiodipropionic acid esters such as di-n- dodecylthiodipropionate'and di-n-octadecyl thiodipropionate; aliphatic sulphides and disulphides such as di-n-dodecyl sulphide, di-n-octadecyl sulphide and di-n-octadecyl disulphide; aliphatic, aromatic or aliphatic-aromaticphosphites and thiophosphites, such as tri-n-dodecyl phosphite, tri(nonyl-phenyl) phosphite, tri-n-dodecyl trithiophosphite, phenyl di-n-decyl phosphite and di-n-octadecyl pentaerithritol diphosphite; UV absorbers such as 2-hydroxy-4- n-octyloxybenzophenone, 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-ditert-butylphenyl 3,5,-ditert butyl-4- hydroxybenzoate, phenylsalicylate, p-tert-butyl-phenylsalicylate, 2,2'-dioctyloxy 5,5'-ditert-butyloxyanilide and 2-ethoxy-5-tert-butyl-2'-ethyloxanilide; nickel stabilisers such as Ni monoethyl 3,5-ditert-butyl- 4-hydroxy- benzylphosphonate, complex butylamine-Ni 2,2'-thiobis (4-tert- octyl- phenolate), Ni 2,2'-thiobis(4-tert- octylphenolphenolate), Ni dibutyl-dithiocarbamate, Ni 3,5-ditert- butyl- 4-hydroxybenzoate, Ni complex of 2- hydroxy-4-n- octyloxybenzophenone; organostannic compounds such as dibutyltin maleate, dibutyltin laurate, dioctyltin maleate; acrylic esters such as ethyl a-cyano, p,,3-diphenyl-acrylate, methyl a-cyano -P- methyl-4methoxycinnamate; metal salts of higher fatty acids such as calcium, barium, cadmium, zinc, lead and nickel stearates, calcium, cadmium, zinc and barium laurates; organic and inorganic pigments such as Colour Index Pigment Yellow 37, Colour Index Pigment Yellow 83, Colour Index Pigment Red 144, Colour Index Pigment Red 48:3, Colour Index Pigment Blue 15, Colour Index Pigment Green 7, titanium dioxide and iron oxides.
The effectiveness as stabilisers of the products prepared according to the invention is illustrated in the following examples in which the products of examples 1 to 7 are used in synthetic polymer compositions.
The results are compared with those obtained from compositions not containing the stabilisers according to the invention and also those compositions containing commercially known stabilisers.
EXAMPLE 8 2.5 g of the compounds produced in Example 1 are dissolved in 100 ml of chloroform are mixed with 1000 g of polypropylene MI = 3.5 ("Moplen" C, ["Moplen" is a register trademark] produced by Montedison), 1 g of n-octadecyl 3-(3,5-di-tert- butyl-4hydroxyphenyl) propionate and 1 g of calcium stearate.
The solvent is removed under vacuum in an oven at a temperature of 50"C over 4 hours.
The dry mixture obtained is then extruded at a temperature of 200"C and transformed into granules from which plates of 0.2 mm thickness are obtained by diecasting at 2000C.
The plates are exposed in a Weather-Ometer 65 WR with a black panel temperature of 63 "C. The increase in the content of carbonyl groups (ACO) is checked periodically using the unexposed samples to compensate for the initial absorption of the polymer.
The time (T 0.1) necessary for giving a ACO% = 0.1 at 5.85 microns is then calculated.
The above procedure was then repeated for each of the compounds prepared in Examples 2-7.
For comparison, a polymer plate is prepared under the same conditions but without adding any of the stabilisers according to the present invention. A plate is also prepared to which 2.5 g of 2-hydroxy-4-n- octyloxybenzophenone, a commercial stabiliser, is added.
Table 1 shows the results obtained.
TABLE I Stabiliser T 0.1 (hours) Comparison test without light stabiliser 200 2-hydroxy-4-n-octyloxybenzophenone 720 Compound of example 1 1670 Compound of example 2 1620 Compound of example 3 1530 Compound of example 4 1760 Compound of example 5 1710 Compound of example 6 1870 Compound of example 7 f690 EXAMPLE 9 2 g of the compounds prepared in Example 1 are dissolved in 100 ml of chloroform and then mixed with 1000 g of high density polyethylene MI = 0.3 ("Moplen" RO, produced by Montedison), 0.5 g of 1,3,5-trimethyl- 2,4,6- tris(3,5-di- tert-butyl-4- hydroxybenzyl) benzene and 1 g of calcium stearate.
The solvent is removed under vacuum in an oven at a temperature of 50"C over 4 hours.
The dry mixture obtained is then extruded at a temperature of 1900C and transformed into granules from which plates of 0.2 mm thickness are obtained by diecasting at 2000C.
The plates are exposed in a "Xenotest" 150 (registered trademark) with a black panel temperature of 60"C and the increase in carbonyl groups (ACO) is checked periodically, using the unexposed samples to compensate for the initial absorption of the polymer. The time (T 0.1) required for giving a ACO% = 0.1 at 5.85 microns is calculated.
The above procedure was then repeated for the compounds obtained in Examples 2-7.
For comparison purposes, polymer plates are prepared under the same conditions: a) without adding a light stabiliser; b) adding 2 g of 2-hydroxy-4- n-octyloxybenzophenone; c) adding 2 g of bis(2,2,6,6- tetramethyl-4- piperidyl)sebacate (commercial stabiliser).
Table 2 shows the results obtained.
TABLE 2 Stabiliser T 0.1 (hours) a) 370 b) 1100 c) 2360 Compound of example 1 3080 Compound of example 2 2890 Compound of example 3 2670 Compound of example 4 3050 Compound of example 5 2930 Compound of example 6 3170 Compound of example 7 2720 EXAMPLE 10 2 g of the compounds obtained in Example 1 are mixed with 100 g of low density polyethylene MI = 0.3 (Pertene ZF 5-1800, produced by Montedison), 0.5 g of 2,6-di- tert-butyl- p-cresol and 1 g of calcium stearate in a low speed mixer.
The mixture obtained is then extruded at 1900C and transformed into granules, from which plates of 0.2 mm thickness are obtained by diecasting at 2000C, and exposed in a "Xenotest" 150 (black panel temperature 60"C.) The time (T 0.5) necessary for giving an increase in the content of carbonyl groups ACO% = 0.5 at 5.85 micron is determined. The above procedure was then repeated for the compounds obtained in Examples 2-7.
For comparison purposes, polymer plates are prepared under the same conditions: a) without adding light stabilisers; b) adding 2 g of 2-hydroxy-4- n-octyloxybenzophenone; c) adding 2 g of bis(2,2,6,6-tetramethyl- 4- piperidyl) sebacate (commercial stabiliser).
The results are given in table 3.
TABLE 3 Stabiliser T 0.5 (hours) a) 1200 b) 2600 c) 3500 Compound of example 1 > 5000 Compound of example 2 > 5000 Compound of example 3 > 5000 Compound of example 4 > 5000 Compound of example 5 > 5000 Compound of example 6 > 5000 Compound of example 7 > 5000 EXAMPLE 11 5 g of the compound prepared in Example 1 are mixed in the same way as described in the previous examples with 100 g of polypropylene MI = 10, 2.5 g of dioctadecyl pentaerithritol diphosphite and 1 g of calcium stearate.
The granules are converted fibres under the following conditions: extruder temperature 230-240"C die temperature 240"C stretching ratio 1: 3 multifilament count 2270/200 den The fibres, mounted on a white card, are exposed until they become fragile in a Weather Ometer 65 WR with a black panel temperature of 63"C.
Other samples of the same fibres are subjected to extraction resistance tests under the following conditions: the fibres, mounted on a stainless steel frame, are immersed in an aqueous solution containing 0.5% of the commercial detergent Dixan which is stirred at a temperature of 80"C.
After 10 hours of treatment, the fibres are rinsed with distilled water, dried and exposed until they become fragile in a Weather-Ometer 65 WR under the conditions already described. The above procedure was then repeated for fibres stabilised with the compounds obtained in Examples 2-7.
As a comparison, polypropylene fibres stabilised with the following substances: a) 5 g of 2-hydroxy- 4-n- octyloxybenzophenone; b) 5 g of bis(2,2,6,6- tetramethyl-4- piperidyl)sebacate as a replacement for the products of the present invention are prepared and treated under the same conditions.
Table 4 shows the results obtained.
TABLE 4 Stabiliser Untreated fibre Washed fibre T fragility (hours) T fragility (hours) a) 720 250 b) 1060 250 Compound of example 1 1290 1200 Compound of example 2 1210 1200 Compound of example 3 1250 1180 Compound of example 4 1350 1250 Compound of example 5 1260 1210 Compound of example 6 1300 1260 Compound of example 7 1170 1030 EXAMPLE 12 5 g of the compound prepared in Example 1 are mixed in the manner described in the previous examples with 1000 g of polypropylene MI = 10, 1 g of 1,3,5-trimethyl -2,4,6-tris(3,5- di-tert-butyl- 4-hydroxybenzyl) benzene (anti-oxidant) and 1 g of calcium stearate.
The granules obtained are converted to fibres under the same conditions as described in example 11.
Polypropylene fibres are prepared with the same additives but without an anti-oxidant.
The fibres obtained are exposed in a forced circulation air oven kept at a temperature of 1200C until they become fragile. The above procedure was then repeated for the compounds of Examples 2-7.
Table 5 shows the results. As a comparison, the results obtained using 5 g of a commercial stabiliser as a replacement for the compounds of the present invention are shown.
TABLE 5 Stabiliser Fragility time (hours) with anti-oxidant without anti-oxidant Compound of example 1 1280 1100 Compound of example 2 1200 ' 1130 Compound of example 3 1120 1070 Compound of example 4 960 880 Compound of example 5 1080 950 Compound of example 6 1370 1200 Compound of example 7 930 860 Bis(2,2,6,6- tetramethyl 4-piperidyl)sebacate 370 320 EXAMPLE 13 Polypropylene fibres are prepared as in example 11, using the following additives per 1000 g of polymer: - 5 g of the compound prepared as in example 1 - 1 g of 1,3,5-tris(3,5- di-tert-butyl- 4-hydrobenzyl)- 1,3,5-triazine- 2,4,6-(1H,3H,5H)trione; - 1 g of calcium stearate - 5 g of the pigments indicated in table 6.
The fibres obtained are exposed until they become fragile in a Weather-Ometer 65 WR (black panel temperature 63"C).
The results a given in table 6, plus a comparison with the data obtained without the light stabiliser.
TABLE 6 Pigments Fragility time (hours) Compound ex. 1 Without light stabiliser TiO2 anatase 1200 180 C.I. Pigment Yellow 37 1120 200 C.I. Pigment Yellow 83 1060 150 C.I. Pigment Red 144 930 110 C.I. Pigment Red 48:3 980 130 C.I. Pigment Blue 15 1300 220 C.I. Pigment Green 7 1270 250 EXAMPLE 14 The low density polyethylene granules prepared as in example 10 are converted to plates of 1 mm. thickness by diecasting at 2000C.
After 48 hours at ambient temperature the appearance of the plates is examined. The presence of stabiliser emerging at the surface clearly indicates low compatibility with the polymer.
The results of these observations are shown in table 7.
TABLE 7 Stabiliser Appearance of the plate Bis(2,2,6,6- tetramethyl-4- Plate is opaque because of the presence piperidyl)sebacate of stabiliser at the surface.
Compound of example 1 Bright plate (complete absence of stabiliser on surface).
Compound of example 2 stabiliser " surface) Compound of example 3 Compound of example 4 Compound of example 5 " Compound of example 6 Compound of example 7 WHAT WE CLAIM IS: 1. Compounds of the general formula
where: R1, R2, which may be the same or different, each represents one atom of hydrogen, a linear or branched alkyl containing 1 to 18 C, a cycloalkyl containing 5 to 18 C, an unsubstituted or substituted aryl containing 6 to 18 C, an arylalkyl containing 7 to 18 C, or a piperidine radical of formula (II):
in which R3,R4,R6,R7, which may be the same or different, each representing an alkyl containing 1 to 6 C, and R5 represents H, O, an alkyl of 1 to 12 C, an alkenyl or alkynyl of 2 to 12 C: X, Y, which may be the same or different, each represent -0-, -S- or
where R8 is H or a linear or branched chain alkyl containing 1 to 18 C, a cycloalkyl containing 5 to 18 C, a substituted or unsubstituted aryl, containing 6 to 18 C, an arylalkyl containing 7 to 18 C, or a piperidine radical of formula (II); the radicals R ,-X-, R2-Y may also represent radicals of nitrogenated heterocyclic compounds of 5 to 8 terms joined to the triazine ring by an atom of nitrogen of said radical; n is a whole number between 7 and 2000; Z represents an n-valent radical obtained by eliminating n atoms of active hydrogen from a linear or branched chain polyamine containing at least 7 primary and/or secondary amino groups, the polyamines containing by repeating units of type:
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (22)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    TABLE 7 Stabiliser Appearance of the plate Bis(2,2,6,6- tetramethyl-4- Plate is opaque because of the presence piperidyl)sebacate of stabiliser at the surface.
    Compound of example 1 Bright plate (complete absence of stabiliser on surface).
    Compound of example 2 stabiliser " surface) Compound of example 3 Compound of example 4 Compound of example 5 " Compound of example 6 Compound of example 7 WHAT WE CLAIM IS: 1. Compounds of the general formula
    where: R1, R2, which may be the same or different, each represents one atom of hydrogen, a linear or branched alkyl containing 1 to 18 C, a cycloalkyl containing 5 to 18 C, an unsubstituted or substituted aryl containing 6 to 18 C, an arylalkyl containing 7 to 18 C, or a piperidine radical of formula (II):
    in which R3,R4,R6,R7, which may be the same or different, each representing an alkyl containing 1 to 6 C, and R5 represents H, O, an alkyl of 1 to 12 C, an alkenyl or alkynyl of 2 to 12 C: X, Y, which may be the same or different, each represent -0-, -S- or
    where R8 is H or a linear or branched chain alkyl containing 1 to 18 C, a cycloalkyl containing 5 to 18 C, a substituted or unsubstituted aryl, containing 6 to 18 C, an arylalkyl containing 7 to 18 C, or a piperidine radical of formula (II); the radicals R ,-X-, R2-Y may also represent radicals of nitrogenated heterocyclic compounds of 5 to 8 terms joined to the triazine ring by an atom of nitrogen of said radical; n is a whole number between 7 and 2000; Z represents an n-valent radical obtained by eliminating n atoms of active hydrogen from a linear or branched chain polyamine containing at least 7 primary and/or secondary amino groups, the polyamines containing by repeating units of type:
    in which R,,Rlo,R11, which may be the same or different, each representing an alkylene of 2 to 12 C, a cycloalkylene of 5 to 12 C, an arylene of 6 to 12 C, an arylalkylene of 7 to 12 C, or a
    -CH2-ÇH-CH2-radical, OH R12 is hydrogen, a linear or branched chain alkyl of 1 to 12 C, a cycloalkyl of 5 to 12 C, a substituted or unsubstituted aryl of 6 to 12 C, an arylalkyl of 7 to 12 C, and m is zero or 1; subject to the condition that in formula (I) the radicals Rl-X- or R2-Y- must contain at least one piperidine radical of formula (II).
  2. 2. A compound according to claim 1, wherein Rl and R2, which may be the same or different, are hydrogen or an alkyl containing 1 to 10 C, a cycloalkyl containing 5 to 10 C, an aryl containing 6 to 10 C, an arylalkyl containing 7 to 10 C, or a piperidine radical of formula (11).
  3. 3. A compound according to claims 1 or 2, wherein R3,R4,R6,R7 each represents a methyl, and R5 is hydrogen or methyl.
  4. 4. A compound according to claims 1, 2 or 3 wherein X and Y, which may be the same or different, are -0-, or
    and R8 is hydrogen, a linear or branched chain alkyl containing 1 to 10 C, a cycloalkyl containing 6 to 10 C or an aryl containing 6 to 10 C, or an arylakyl containing 7 to 10 C or a piperidine radical of formula (II).
  5. 5. A compound according to any one of the preceding claims wherein Z is the residue of a polyamine containing the repeating units
    wherein R9,Rlo and R11, which may be the same or different, are each a C2-C6 alkylene, a C6-Cl0 cycloalkylene, a C6-C10 arylene, a C7-C10 arylalkylene, or the
    -CH2-CH-CH2- group, OH R12 is hydrogen or a Cl-C6 alkyl, and m is zero or 1.
  6. 6. A compound according to claim 1, wherein X, Y are -0, > NH, > N-alkyl of 1 to 6 C, or > N-Pip, Pip being 2,2,6,6-tetramethyl-4- piperidyl, R1, R2 are hydrogen, an alkyl of 1 to 6 C or a 2,2,6,6-tetramethyl -4-piperidyl, R,R4,R6, R7 are all methyls, R5 is hydrogen, R9 Rlo and R 1 l, which may be the same or different, are each a C2-C6 alkylene or the
    group; R12 is hydrogen, m is 1, and n lies between 7 and 500.
  7. 7. A compound according to claim 1, wherein Z is the residue of a linear or branched polyamine obtained by polymerising ethyleneimine.
  8. 8. A compound according to claim 1, wherein Z is the residue of a linear or branched polyamine obtained by condensing hexamethylenediamine with epichlorohydrin.
  9. 9. A method of preparing a compound of the formula:
    wherein R1, R2, X, Y, Z and n are as defined in Claim 1, comprising reacting 4,6-disubstituted -2-halo-1,3,- 5-triazine with a polyamine containing a repeating unit of the formula:
    wherein -Rg, Rlo, R11, R12 and m are as defined in Claim 1.
  10. 10. A method according to Claim 9 wherein said halogen is chlorine.
  11. 11. A method according to claim 9 or 10 wherein said reaction is carried out in the presence of an inert solvent.
  12. 12. A method according to claim 10 wherein said solvent is acetone, dioxane, toluene or xylene.
  13. 13. A method according to claim 9, 10 or 11 wherein said reaction is carried out in the presence of an inorganic or organic base.
  14. 14. A method according to claim 13 wherein said base is triethylamine, tributylamine, sodium hydrate, sodium carbonate, sodium bicarbonate, potassium hydrate or potassium bicarbonate.
  15. 15. A composition comprising a synthetic polymer and a stabilising compound of the formula (I) as claimed in claim 1 wherein said stabilising compound is used in quantity between 0.1 and 5% by weight of said synthetic polymer.
  16. 16. A composition according to claim 15 wherein said synthetic polymer is high density polyethylene, low density polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinylacetate copolymers, butadiene-styrene copolymers, acrylonitrile-butadienestyrene copolymers, polyethylene terephthalate or unsaturated polyesters.
  17. 17. A composition according to claim 16 wherein said synthetic polymer is high density polyethylene or low density polyethylene.
  18. 18. A composition according to claim 16 wherein said synthetic polymer is polypropylene.
  19. 19. A composition according to claim 15 wherein said quantity of stabilising compound is between 0.1 and 1 % by weight of said synthetic polymer.
  20. 20. A composition according to claims 15 to 18 wherein said synthetic polymer is in the form of a fibre, monofilament, stretched tape, film or moulded object.
  21. 21. A method of preparing a compound of formula (I) according to claim 9 substantially as described by examples 1 to 7.
  22. 22. A composition according to claim 15 substantially as described in examples 8 to 14.
GB4726077A 1976-11-26 1977-11-14 Stabilisers for synthetic polymers and a process for their preparation Expired GB1580940A (en)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
GB2266531A (en) * 1992-04-14 1993-11-03 Ciba Geigy Ag Novel piperidine-triazine co-oligomers for use as stabilisers for organic materials
GB2377704A (en) * 1998-12-14 2003-01-22 Ciba Sc Holding Ag Sterically hindered amine compounds

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US4234707A (en) * 1977-11-10 1980-11-18 Ciba-Geigy Corporation Polymeric light stabilizers for plastics
DE2961381D1 (en) * 1978-02-08 1982-01-28 Ciba Geigy Ag Polyalkylpiperidine derivatives of s-triazines, their use as stabilizers for polymers and polymers thus stabilized
EP0013682B1 (en) * 1979-01-29 1981-10-14 Ciba-Geigy Ag Piperidyl-triazine derivatives, process for their production, their use as stabilizers for polymers and the polymers stabilized therewith
DE2933078A1 (en) * 1979-08-16 1981-03-26 Hoechst Ag, 65929 Frankfurt NEW TRIAZINE DERIVATIVES, THEIR PRODUCTION AND THEIR USE AS STABILIZERS FOR SYNTHETIC POLYMERS
DE2944729A1 (en) * 1979-11-06 1981-05-14 Hoechst Ag, 6000 Frankfurt NEW TRIAZINE STABILIZERS
DE3022896A1 (en) * 1980-06-19 1981-12-24 Hoechst Ag, 6000 Frankfurt POLYTRIAZINYLAMINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS STABILIZERS FOR SYNTHETIC POLYMERS
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
DE3113455A1 (en) * 1981-04-03 1982-10-21 Hoechst Ag, 6000 Frankfurt POLY-BIS-TRIAZINYLIMIDES, THEIR PRODUCTION, THEIR USE AS LIGHT PROTECTION AGENTS FOR POLYMERS AND THE POLYMERS STABILIZED WITH THEM
IT1195277B (en) * 1981-10-02 1988-10-12 Chimosa Chimica Organica Spa PIPERIDIL DERIVATIVES OF MACROCYCLIC TRIAZIN COMPOUNDS, HAVING STABILIZING ACTIVITY FOR POLYMERS AND PROCESSES FOR THEIR PREPARATION
IT1152192B (en) * 1982-05-19 1986-12-31 Apital Prod Ind COMPOUNDS FOR STABILIZING POLYMERS
ATE415448T1 (en) * 2001-11-30 2008-12-15 Ciba Holding Inc 2-HYDROXYPHENYL-S-TRIAZINE CROSSLINKER FOR POLYMER NETWORKS

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GB1393551A (en) * 1972-04-21 1975-05-07 Ciba Geigy Ag Piperidine derivatives
SE412071B (en) * 1975-03-21 1980-02-18 Montefibre Spa STABILIZED POLYOLEFINE-BASED POLYMER COMPOSITIONS AND SIMILAR STABILIZER
IT1060458B (en) * 1975-12-18 1982-08-20 Chimosa Chimica Organica Spa TRIAZIN PIPERIDYL COMPOUNDS SUITABLE FOR THE STABILIZATION OF SYNTHETIC POLYMERS AND PROCEDURE FOR THEIR PREPARATION

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2266531A (en) * 1992-04-14 1993-11-03 Ciba Geigy Ag Novel piperidine-triazine co-oligomers for use as stabilisers for organic materials
GB2266531B (en) * 1992-04-14 1996-03-13 Ciba Geigy Ag Novel piperidine-triazine co-oligomers for use as stabilisers for organic materials
GB2377704A (en) * 1998-12-14 2003-01-22 Ciba Sc Holding Ag Sterically hindered amine compounds
GB2377704B (en) * 1998-12-14 2003-06-18 Ciba Sc Holding Ag Sterically hindered amine compounds

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ES464469A1 (en) 1978-09-01

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