CA2033672C - Melamine derivatives as stabilisers for chlorine-containing polymers - Google Patents
Melamine derivatives as stabilisers for chlorine-containing polymers Download PDFInfo
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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- 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
- C08K5/34922—Melamine; Derivatives thereof
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Abstract
Compositions containing a) a chlorine-containing polymer, b) 0.01 to 1% by weight, relative to the chlorine-containing polymer, of a compound of the formula I and/or its hydrochloride, in which R is C6-C20alkyl, C3-C20alkyl interrupted by 1 to 5 oxygen atoms, C1-C20alkyl substituted by 1 to 5 OH, C3-C20alkenyl, C3-C8cycloalkyl, C1-C4alkyl-substituted C3-C8Cycloalkyl, C7-C11phenylalkyl, C7-C11phenylalkyl which is substituted on the phenyl by 1 to 3 radicals, these radicals, independently of one another, being hydroxyl, chlorine, Ct-C4alkyl, methoxy or ethoxy, or R is furthermore a group of the formula IIa or IIb, in which X is C1-C20alkyloxy, C1-C20alkylthio, phenyloxy, phenylthio, benzyloxy or benzylthio, and R1, R2 and R3, independently of one another, are hydrogen, C1-C20alkyl, C1-C20alkyloxy, C1-C20alkylthio, C2-C12alkyloxycarbonyl, C2-C12alkanoyl, phenyl, phenyloxy, phenylthio, hydroxyl, mercapto or chlorine, and c) 0.01 to 5% by weight, relative to the chlorine-containing polymer, of an Me(II) carboxylate and/or Me(II)-phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
Some of the compounds of the formula I are novel.
Some of the compounds of the formula I are novel.
Description
A-17906/+/CGM 328 Melamine derivatives as stabilisers for chlorine-containing polymers The present invention relates to compositions containing a) a chlorine-containing polymer, b) a melamine derivative and c) a metal salt, to the use of a mixture comprising components b) and c) for stabilising a chlorine-containing polymer against thermal degradation and to novel melamine derivatives.
It is known that chlorine-containing polymers have to be protected against the damaging effect of light and heat, in particular during the processing to give moulded articles. A few melamine derivatives and their use as stabilisers for chlorine-containing polymers are described, for example, in JP-A-Sho 56/43,342, US-A 3,084,135 and US-A
3,496,136.
The preparation of various melamine derivatives has already been described by D.F.
Walker et al.; "J. Am. Pharm. Ass. 39, 393-396", 1951 by D.W. Kaiser et al.;
"J. Am.
Chem. Soc. 73, 2984-2986", 1963, by D.lr. O'Brien et al.; "J. Med. Chem. 6, 467-471", 1967 by Smolin et al.; "s-Triazines and Derivatives - The Chemistry of Heterocyclic Compounds, Chapter VI, pp. 309-388" and also in 1967 by A.B. Borkovec et al.;
"J. Med.
Chem. 10, 457-461" and in US-A 4,312,988. Melamine derivatives as odour-binding agents for polyvinyl chloride films are known from JP-A 79/6043 and JP-A
86/116,512.
The present invention relates to compositions containing a) a chlorine-containing polymer, b) O.U1 to 1% by weight, relative to the chlorine-containing polymer, of a compound of the formula I and/or its hydrochloride, NHR
N i _N
(I) H2N ~N NH2 in which R is C6-CZOalkyl, C3-C2oalkyl interrupted by 1 to S oxygen atoms, Ct-C2oalkyl ~~~~~~~2 substituted by 1 to 5 OIi, C3-C2«alkenyl, C3-Cscycloalkyl, CI-Cnalkyl-substituted C3-C$cycloalkyl, C~-CI tphenylalkyl, C~-Cl tphenylalkyl which is substituted on the phenyl by 1 to 3 radicals, these radicals, independently of one another, being hydroxyl, chlorine, CI-Cnalkyl, methoxy or ethoxy, or R is furthermore a group of the formula IIa or IIb, -CH2-CH-CF12-X , I
(ITa) (IIb) in which X is Ct-C2oalkyloxy, Ct-C2oalkylthio, phenyloxy, phenylthio, benzyloxy or benzylthio, and Rt, R2 and R3, independently of one another, are hydrogen, C1-CZOalkyl, Ct-C2oalkyloxy, Cl-C2oalkylthio, C2-Cl2alkyloxycarbonyl, C2-Cl2alkanoyl, phenyl, phenyloxy, phenylthio, hydroxyl, mercapto or chlorine, and c) 0.01 to 5% by weight, relative to the chlorine-containing polymer, of an Me(II) carboxylate and/or Me(II)-phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
Component c) is preferably a mixture of Ba/Zn carboxylates if component b) is phenyl-melamine.
Examples of R as C6-C2oalkyl are hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl.
R as C3-Gioalkyl which is interrupted by 1 to 5 oxygen atoms is preferably a group of the formula CrH2r- Z , s in which r is 2 or 3, s is 1, 2, 3, 4 or 5, and Z is, for example, methyl, ethyl, propyl or butyl.
4~'~t~~~
It is known that chlorine-containing polymers have to be protected against the damaging effect of light and heat, in particular during the processing to give moulded articles. A few melamine derivatives and their use as stabilisers for chlorine-containing polymers are described, for example, in JP-A-Sho 56/43,342, US-A 3,084,135 and US-A
3,496,136.
The preparation of various melamine derivatives has already been described by D.F.
Walker et al.; "J. Am. Pharm. Ass. 39, 393-396", 1951 by D.W. Kaiser et al.;
"J. Am.
Chem. Soc. 73, 2984-2986", 1963, by D.lr. O'Brien et al.; "J. Med. Chem. 6, 467-471", 1967 by Smolin et al.; "s-Triazines and Derivatives - The Chemistry of Heterocyclic Compounds, Chapter VI, pp. 309-388" and also in 1967 by A.B. Borkovec et al.;
"J. Med.
Chem. 10, 457-461" and in US-A 4,312,988. Melamine derivatives as odour-binding agents for polyvinyl chloride films are known from JP-A 79/6043 and JP-A
86/116,512.
The present invention relates to compositions containing a) a chlorine-containing polymer, b) O.U1 to 1% by weight, relative to the chlorine-containing polymer, of a compound of the formula I and/or its hydrochloride, NHR
N i _N
(I) H2N ~N NH2 in which R is C6-CZOalkyl, C3-C2oalkyl interrupted by 1 to S oxygen atoms, Ct-C2oalkyl ~~~~~~~2 substituted by 1 to 5 OIi, C3-C2«alkenyl, C3-Cscycloalkyl, CI-Cnalkyl-substituted C3-C$cycloalkyl, C~-CI tphenylalkyl, C~-Cl tphenylalkyl which is substituted on the phenyl by 1 to 3 radicals, these radicals, independently of one another, being hydroxyl, chlorine, CI-Cnalkyl, methoxy or ethoxy, or R is furthermore a group of the formula IIa or IIb, -CH2-CH-CF12-X , I
(ITa) (IIb) in which X is Ct-C2oalkyloxy, Ct-C2oalkylthio, phenyloxy, phenylthio, benzyloxy or benzylthio, and Rt, R2 and R3, independently of one another, are hydrogen, C1-CZOalkyl, Ct-C2oalkyloxy, Cl-C2oalkylthio, C2-Cl2alkyloxycarbonyl, C2-Cl2alkanoyl, phenyl, phenyloxy, phenylthio, hydroxyl, mercapto or chlorine, and c) 0.01 to 5% by weight, relative to the chlorine-containing polymer, of an Me(II) carboxylate and/or Me(II)-phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
Component c) is preferably a mixture of Ba/Zn carboxylates if component b) is phenyl-melamine.
Examples of R as C6-C2oalkyl are hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl.
R as C3-Gioalkyl which is interrupted by 1 to 5 oxygen atoms is preferably a group of the formula CrH2r- Z , s in which r is 2 or 3, s is 1, 2, 3, 4 or 5, and Z is, for example, methyl, ethyl, propyl or butyl.
4~'~t~~~
Examples of R as Ct-CZOalkyl which is substituted by 1 to 5 OH are hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 2-hydroxypentyl, 2,3,4,5,6-pentahydroxyhexyl, 8-hydroxyoctyl, 2-hydroxyoctyl, 2-hydroxynonyl, 2-hydroxydecyl or 2-hydroxyoctadecyl. Ci-Cghydroxyalkyl in which the hydroxyl group is in the terminal position or in the 2-position is preferred as is C~-CZOalkyl which is substituted by -OH in the 2-position. Ct-Cbalkyl which is substituted by -OH is particularly preferred.
Examples of R as C3-C2oalkenyl are allyl, 2-methallyl, 3-methylbut-2-enyl, 3-methylbut-3-enyl, hexenyl, decenyl, undecenyl, heptadecenyl or oleyl.
Preferred meaning~~ are allyl, methallyl and oleyl.
Examples of R as C3-CBCycloalkyl which is unsubstituted or substituted by Ct-C4alkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 4-butylcyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. CS-C~cycloalkyl, in particular cyclohexyl, is preferred.
R as C~-(a tphenylalkyl is, for example, benzyl or phenylethyl.
Example., of R as C~-Citphenylalkyl which is substituted by 1 to 3 radicals according to the definition are o-, m- or p-chlorobenzyl, 2,3-dichlorobenzyl, 2,4-dichlorobenzyl, 2,5-dichlorobenzyl, 2,6-dichlorobenzyl, 3,4-dichlorobenzyl, 2,4,5-trichlorobenzyl, 2,4,6-trichlorobenzyl, o-, m- or p-hydroxybenzyl, o-, m- or p-methylbenzyl, 2,3-dimethylbenzyl, 2,4-dimethylbenzyl, 2,5-dimethylbenzyl, 2,6-dimethylbenzyl, 3,4-dimethylbenzyl, 3,5-dimethylbenzyl, 2-methyl-4-tart-butylbenzyl, 2-ethylbenzyl, 2,6-diethylbenzyl, 2,6-diethyl-4-methylbenzyl, 2,6-diisopropylbenzyl, 4-tent-butylbenzyl, 2-chloro-6-methylbenzyl, 3-chloro-2-methylbenzyl, 3-chloro-4-methylbenzyl, 4-chloro-2-methylbenzyl, 5-chloro-2-methylbenzyl, 2,6-dichloro-3-methylbenzyl, 2-hydroxy-4-methylbenzyl, 3-hydroxy-4-methylbenzyl, o-, m- or p-methoxybenzyl, o-, m-or p-ethoxybenzyl, 2,4-dimethoxybenzyl, 2,5-dimethoxybenzyl, 2,5-diethoxybenzyl, 2-methoxy-5-methylbenzyl, 4-methoxy-2-methylbenzyl, 3-chloro-4-methoxybenzyl, 3-chloro-6-methoxybenzyl, 3-chloro-4,6-dimethoxybenzyl or 4-chloro-2,5-dimethoxybenzyl.
Examples of Rt, R2 and R3 as Ct-C2oalkyl are, in addition to the meanings given above for R = alkyl, methyl, ethyl, propyl, isopropyl, butyl, ten-butyl, pentyl, hexyl and heptyl.
Examples of X, Rt, R2 and R3 as Ct-CZOalkyloxy are methoxy, ethoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, tridecyloxy, hexadecyloxy or octadecyloxy. One of the preferred meanings for Rt, RZ and R3 is Ct-C4alkyloxy, in particular methoxy and ethoxy.
Examples of X, Rt, RZ and R3 as Ct-C2oalkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, dodecylthio, tridecylthio, hexadecylthio or octadecylthio. C8-CtBalkylthio is preferred.
Examples of Rt, RZ and R3 as C2-Ct2alkyloxycarbonyl are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, octyloxp:arbonyl and decyloxycarbonyl.
Examples of Rt, R2 and R3 as C2-Ct2alkanoyl are acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl or decanoyl.
Example: of group IIb are o-, m- or p-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 3,4-dichlorophenyl, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl, o-, m- or p-hydroxyphenyl, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-4-ten-butylphenyl, 2-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl, 3,5-diethylphenyl, 2,6-diethyl-4-methylphenyl, 2,6-diisopropylphenyl, 4-tent-butylphenyl, 3,5-di-tett-butylphenyl, 2-chloro-6-methylphenyl, 3-chloro-2-methylphenyl, 3-chloro-4-methylphenyl, 4-chloro-2-methylphenyl, 5-chloro-2-methylphenyl, 2,6-dichlaro-3-methylphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m-or p-propoxyphenyl, o-, m- or p-butoxyphenyl, o-, m- or p-hexyloxyphenyl, o-, m- or p-octyloxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,5-diethoxyphenyl, 2-methor:y-5-methylphenyl, 4-methoxy-2-methylphenyl, 3-ehloro-4-methoxyphenyl, 3-chloro-6-methoxyphenyl, 3-chloro-4,6-dimethoxyphenyl, 4-chloro-2,5-dimethoxyphenyl, o-, m- or p-methylthiophenyl, o-, m- or p-ethylthiophenyl, o-, m- or p-propylthiophenyl, o-, m- or p-butylthiophenyl, o-, m- or p-pentylthiophenyl, o-, m- or p-hexylthiophenyl, o-, m- or p-heptylthiaphenyl, o-, m- or p-octylthiophenyl, o-, m-or p-nonylthiophenyl, o-, m- or p-decylthiophenyl, o-, m- or p-phenylphenyl and 2-hydroxy-4-methylphenyl, 3-hydroxy-4-rnethylphenyl and a group of the formula ct-c4-alkyl / \ oft C t-C4-alkyl Preferred meanings for group IIb can be seen from Examples 1 to g given below.
In the group of the formula IIb, R1 and/or R2 are particularly prefererably hydrogen.
Compositions which are of interest are those in which R is Cto-Ctg-alkyl, OH-substituted Cl-Cloallcyl, C3-Ctoalkenyl, CS-C~cycloalkyl, Ct-C4alkyl-substituted Cg-C~cycloalkyl, benzyl, benzyl which is substituted on the phenyl by 1 to 3 radicals, these radicals, independently of one another, being hydroxyl, chlorine, Ct-C4alkyl, methoxy or ethoxy, or R is furthermore a group of the formula lIa or IIb, in which X is Ct-Ctoalkyloxy, Cg-CtBalkylthio, phenyloxy, phenylthio, benzyloxy or benzylthio and Rt, R2 and R3, independently of one another, are hydrogen, Ct-Ctoalkyl, Ct-Ctoalkyloxy, Cg-CtBalkylthio, C2-Ct2alkyloxycarbonyl, C2-C6alkanoyl, phenyloxy, phenylthio, hydroxyl, mercapto or chlorine.
Compositions in which R is Cto-Ctgalkyl, OH-substituted Ct-C6alkyl, allyl, cyclohexyl or benzyl are also of interest.
R is preferably the group lIb.
Preference is also given to compositions in which R is a group of the formula IIb and the radicals Rt, R2 and R3, independently of one another, are hydrogen, Ct-C4alkyl, Ct-C4alkyloxy, Cg-Ct6alkylthio, C2-Ct2alkyloxycarbonyl, hydroxyl, mercapto or chlorine.
Particulw preference is given to compositians in which R is a group of the formula IIb, RI
is hydrogen, R2 and Rg, independently of one another, are Cl-C4alkyl, Ci-C4a(kyloxy, Cg-Ctbalkylthio, C2-Ct2alkyloxycarbonyl, hydroxyl or chlorine and RZ is additionally hydrogen.
Compositions which are of particular interest are those in which R is a group of the formula IIb, Rt and R2 are hydrogen and R3 is CI-C4alkyl, Ct-C4alkyloxy, Cg-Ctbalkylthio, C2-CF2alkyloxycarbonyl, hydroxyl or chlorine, in particular CF-C4alkyloxy or hydroxyl.
According to a further preference, component b) can be present as hydrochloride.
Componc;nt c) is preferably an Me(II) carboxylate, in which Me(II) is Ba, Ca, Mg, Cd or Zn. The c:arboxylates are preferably salts of carboxylic acids having 7 to 20 C atoms, for example benzoates, alkanoates or alkenoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or 2-ethylhexanoates. Stearates, oleates or p-tert-bmylbenzoates are particularly preferred.
Mixtures of Ba/Zn or CalLn carboxylates are also particularly preferred as component c).
An Me(Il) phenolate as component c) is in particular a C~-CZp(o-, m- or p-)alkylphenolate, for example o-, m- or p-nonylphenolate.
According to a further preference, the compositions according to the invention contain an epoxy compound and/or a phosphite as additional component d).
The epoxy compound is preferably an epoxidised oil or an epoxidised fatty acid ester, for example epoxidised soya bean oil, epoxidised butyl oleate and epoxidised octyl oleate.
The phosphites are preferably those of the formula Al0 O O Al0 CH3 \ / \ \ t A20-P, Al0-P P-OAZ, P-OCH2CH O, P-OCH2CHOCHCH2 , \ / / ~ i i A30 O O A30 2 OAt CH3 CH3 n in which A1, A2 and A3, independently of one another, are C4-Ctgalkyl, C6-Ctgalkenyl, CS-C~cycloalkyl, phenyl or phenyl which is substituted by one to three Ct-Ct2alkyl groups.
Examples are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite. Preference is given to the aryl _7_ dialkyl and the alkyl diaryl phosphates, for example phenyl didecyl, (2,4-di-ten-butylphenyl) didodecyl, (2,6-di-tcrt-butylphenyl) didodecyl phosphate and the dialkyl and diaryl pentacrythritol diphosphitcs, for example distearyl pentaerythritol diphosphite. Preference is also given to the tetrapheny:l and tetraalkyl [1,2-dipropylene glycol] diphosphites and the poly[1,2-dipropylene glycol phenyl phosphates]
and the poly[1,2-dipropylene glycol alkyl phosphates].
Particularly preferred organic phosphates are distearyl pentaerythritol diphosphite, tris(nonylphenyl)phosphite, phenyldidccylphosphite, tetraphenyl [1,2-dipropylene glycol]
diphosphite and poly[1,2-dipropylene glycol phenyl phosphate].
The Me(II) carboxylates or phenolates are preferably used in amounts of 0.05 to 5% by weight.
The phosphates are used, for example, in concentrations of 0.3 to 5, preferably 0.5 to 1, by weight, and the epoxy compounds, for example epoxidised soya bean oil, advantageously in concentrations of 1 to 8, preferably 1 to 3, % by weight.
The compounds of the formula I are preferably incorporated in the chlorine-containing polymer in amounts of 0.05 to 1 or 0.01 to 0.9, in particular 0.1 to 0.7, % by weight.
The % by weight given refers in each case to the material to be stabilised.
The chlorine-containing polymers are preferably vinyl chloride homopolymers or copolymers. Examples of suitable comonomers for the copolymers are: vinyl acetate, vinylidene chloride, trans-dichloroethene, ethylene, propylene, butylene, malefic acid, acrylic acid, fumaric acid, itaconic acid. Further suitable chlorine-containing polymers are postchlorinated PVC and chlorinated polyolefins, furthermore graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of the abovementioned homo-and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, in particular with ABS, MBS, NBR, SAN, EVA.
Further preference is given to suspension and bulk polymers and to emulsion polymers.
Polyvinyl chloride is particularly preferred as chlorine-containing polymer.
_g_ The invention further relates to the use of a stabiliser system containing components b) and c) for stabilising a chlorine-containing polymer against thermodegradation.
Depending on the intended use of the polymers, further additives can be incorporated before or during the incorporation of the stabilisers, for example phenolic antioxidants, lubricants (preferably montan waxes or glycerol esters, fatty acid esters, paraffins, amide waxes, stear-ic acid, mono- and dihydroxystearic acid, higher fatty alcohols), plasticisers, fillers, carbon black, asbestos, kaolin, talc, glass fibres, modifiers, (impact-resistant additives), processing aids (for example polymethacrylic esters), fluorescent whitening agents, pigments, light stabilisers, ster-ically hindered amines, UV
absorbers, flame retardant;> or antistatics.
Further possible additives are furthermore f3-aminocrotonates, for example the compounds described in DE-A 804,442, DE-A 807,207 and JP-A 75/17,454, pyrroles, for example the compounds mentioned in EP-A 22,087, aminouracils, for example the compounds disclosed in EP-A 65,934, aminothiouracils, for example the compounds known from EP-A 41,479, polyols, for example the compounds described in DE-A 3,019,910, f3-diketones, for example the compounds mentioned in DE-A 2,600,516, hydrotalcites, in particular the compounds described in DE-A 3,843,581, or also mixtures of f3-diketones and hydrotalcites, as described in EP-A 63,180, furthermore Mg/Al carbonates, for example the Mg/Al carbonates disclosed in JP-A-Sho 62/267,347 (=Chemical Abstracts 108:168 635 h), and Alcamizers, for example 4 Mg0 A1203.C02.9 H20, 4 Mg0 Ai2O3.C02.6 H20, Zn0 3MgU A1203.C02.8-9 H20, Zn0 3 Mg0 A1203.C02.5-6 H20 and Mg4A12(t~H)12(C03)t-Xn(C104)xmH20.
Possible additives are also chemical blowing agents for expanded rigid or plasticised polyvinyl chloride, for example NaHC03 and the blowing agents mentioned in "Gachter,~iVliiller; Taschenbuch der Kunststoff-Additive (Handbook of plastic additives), Carl Hanser Verlag Munich-Vienna, 2nd edition, 1983" on page 651.
The stabiliser components are most favourably incorporated in the chlorine-containing polymer, as is usual, on mixed rolls, for example in a 2-roll mill at temperatures between 150° and 200°C. In general, sufficient homogenisation can be obtained within 5 to 1S
minutes. The components can be added individually or together as a premixture.
A liquid premixture has proven to be advantageous, i.e, the homogenisation is carried out in the presence of inert solvents and/or plasticisers.
~~.~~~~' The compositions according to the invention can be processed to give moulded articles by the moulding processes customary for this, for example by extrusion, injection-moulding or calandering. The use of plastisols is also possible.
The compositions according to the invention are preferably used for the manufacture of electro cables, hollow articles, for example pipes, and in particular sheets in the automobile industry. This use is also provided by the invention. A
particularly preferred area of application is the manufacture of sheets for the interior of automobiles, in particulw for those as described in DE-A 3,227,107 and DE-A 3,401,482.
The compositions according to the invention are particularly advantageously used for the manufacture of deep-drawing sheets and flexible sheets based on PVC, in particular for the use in the automobile industry.
The compounds of the formula I can be prepared in analogy to known processes.
Preparation processes are described, for example, in the following publications: D.F.
Walker et al.; J. Am. Pharm. Assoc. 39, 393 (1950), D.W. Kaiser et al.; J. Am.
Chem. Soc.
73, 2984 ( 1951 ), A.B. Borkovec et al.; J. Med. Chem. 10, 457 ( 1967). ' When R has one of the abovementioned meanings other than the group IIb, it is advantageous to prepare the melamine derivatives by the following scheme:
Scheme ~~
Cl i N N base N N
+ RNH~ ---~ ~ + HC1 H2N Y NH2 H2N \N NH2 In general, water is a suitable reaction medium. In some cases, in particular if R is a long-chain allcyl radical, it is advantageous to add a solubiliser, for example dirnethyhicetamide. The base is, for example, alkali metal hydroxide, preferably sodium hydroxid.~.
The melamine obtained can be converted to the corresponding hydrochloride by heating it ~~~ta~~
with concentrated hydrochloric acid (slight excess). Inversely, it is possible to obtain again the melamine from the hydrochloride by treating with, for example, alkali metal hydroxide or alkali metal bicarbonate solution, which would constitute a further purification step.
In some eases, it is also possible to prepare compounds of the formula I in which R is a group of the formula IIb by the above scheme A; however, in these cases, the basicity of the amine; must be higher.
Compounds of the formula I in which R is a group of the formula IIb are preferably prepared by Scheme B given below.
Scheme 13:
Cl NHR
N /~ N HCl N ~ N
+ RNH2 ----~ ~ HCl In this case, too, water is a suitable reaction medium, it being possible, if required, to add again a solubiliser. The hydrochloride is advantageously converted into the corresponding melamine; derivative as described above.
In general, the compounds of the formula I and their hydrochlorides have a defined hydrated water content.
The starting materials are commercially available or can be prepared in analogy to processes known to one skilled in the art. The preparation of diaminochlorotriazine is described, for example, by J.T. Thurston et al. in "J. Am. Chem. Soc. 73, 2981 (1951)".
The compounds of the formula I can also be used against photolytic degradation of chlorine-containing polymers.
The invention also relates to the novel compounds of the formula Ia and hydrochlorides thereof, NIiR
N i 'N
(la) HZN \N NHZ
in which R is C~-Cttphenylalkyl which is substituted on the phenyl by 1 to 3 radicals, the radicals, independently of one another, being hydroxyl, chlorine, Ct-C4alkyl, methoxy or ethoxy, or R is furthermore a group of the formula lIa, II-b-1, II-b-2 or II-b-3, Y1 . ~ Y4.
- CH2- CH- CH2-X , I
Y3 1'6 Y9 (IIa) (II-b-1) (II-b-2) (II-b-3) in which X is Cl-C2oalkyloxy, Ct-C2oalkylthio, phenyloxy, phenylthio, benzyloxy or benzylthio, Yt, Y2 and Y3, independently of one another, are Ct-Czoalkylthio, C2-Ct2allcyloxycarbonyl or mercapto, and Yt and Y2 are additionally hydrogen, Y4 is methoxy, ethoxy or hydroxyl, YS and Y6, independently of one another are Ct-C2palkyl, Ct-C2palkyloxy, Cl-CZpalkylthio, C2-Ct2alkyloxycarbonyl, C2-Ct2alkanoyl, phenyl, phenyloxy, phenylthio, hydroxyl, mercapto or chlorine, and YS is additionally hydrogen, Y~, Yg and Y9, independently of one another, are C2-C2ealkyl or C2-Ct2alkyloxycarbonyl and Yg is additionally hydrogen.
For the compounds of the formula Ia, the same preferences apply as for the compounds of the formula I, and the radicals Yt to Y9 correspond to the radicals Rt to R3.
The examples which follow illustrate the invention in more detail. Parts and percentages are by weight, unless stated otherwise.
Example 1: Preparation of N-(n-dodecyl)melamine (Com_pound 1-A-1).
A mixture of 14.6 g (0.1 mol) of diaminochlorotriazine, 19.5 g (0.105 mol) of n-dodecylamine and 4.0 g (0.1 mol) of sodium hydroxide in 200 ml of water is refluxed for 5 hours. The solid formed is filtered off with suction, washed until free of chloride and then treated with a mixture of methylene chloride/ether (1:1). The precipitate is filtered off and boiled in dimethylformamide. After filtration, the concentrated filtrate is poured into ~, 5'~ F~ (''~ f ~~e~c.7~
water with stirring. The precipitate formed is dried to constant weight. The yield is 65% of theory. The product contains 0.1 mol of hydrated water per mole of melamine and melts at 119°C.
Example 2: The compounds in Table 1 are prepared in analogy to the process described in Example 1.
Table l:
NHR
N i 'N
H2N~N- _NH2 Compound No. R Melting Yield [% of theory]
point 1-A-2 -(CH2)3-OH160C 87 1-A-3 -(CH2)5-OH- -1-A-4 -CH2-CH=CH2172C 57.2 (The product is present in the form of a hydrate (0.25 mol of H20 per mol of melamine).
66 (After recrystallisation from acetic acid. The product is present in the 1-A-$ ~ 146 C
form of a hydrate (0.6 mol of F120 per mol of melamine).) i ~ i i 2J P~ ~ r9 Example 3: Preyaration of N-benzylmelamine ~drochloride (Com-pound 1-A-7) 10.8 g (0.05 mol) of compound 1-A-6 are refluxed tol;ether with 6.84 g (0.06 mol) of 32%
hydrochloric acid for 1 hour with stirring. The clear solution is Gaoled to 0°C, and the crystals formed are filtered off, washed and dried. The yield is 73.8% of theory. The product has a melting point of 275°C.
Example 3a: Preparation of N-f3-(2'-ethylhexyl)oxy-2-hydroxypropyllmelami_ne Com ound 1A-8).
A mixture of 29.1 g (0.2 mol) of diaminochlorocriazine, 40.7 g (0.2 mol) of 3-(2'-ethylhexyl)oxy-2-hydroxypropylamine and 300 ml of water is refluxed. 0.2 mol of NaOH in 80 ml of water are added dropwise over a period of 1 hour. The reaction mixture is then refluxed for 2 hours. 25 ml of concentrated hydrochloric acid are added to the resulting oil, giving a clear solution. Upon cooling, the hydrochloride of N-[3-(2'-ethylhexyl)oxy-2-hydroxypropyl]melamine precipitates and is ehen neutralised with NaFIC03 at 40°C. The wax-like product obtained is washed until free of chloride with ice water and dried in vacuo. The yield is 86.6% of theory. The product has a melting point of 1.09 - 115°C.
Example 3b: Preparation of N-n-hexylmelamine (Compound 1-A-9).
The prep;~ration is carried out in analogy to Example 3a. The yield is 70.8%
of theory. The product has a melting point of 116-119°C.
Example 4: Preparation of N-phenylmelamine (= Compound 2-A-1) A mixture of 14.6 g (0.1 mol) of diaminochlorotriazine, 9.8 g (0.105 mol) of aniline and 4.0 g (0.1 mol) of sodium hydroxide in 30 ml of water is refluxed for 2 hours with the addition of 200 ml of water. The cloudy solution is cooled, the precipitated solid is filtered off, washed until free of chloride and dried to constant weight. The product obtained is purified by dissolving it in glacial acetic acid and then treating it with bicarbonate. The yield is 62% of theory. The product has a melting point of 202°C.
Example 5: The compounds listed in Tables 2a to 2c are prepared in analogy to the process described in Example 4. The data given in Tables 2a to 2c refer to the general formula liven below.
ih!
NHR
N i 'N . (HCI)n H2N ~ N ~ NH2 Table 2a;
Comp. n R Melting point Yield [3'0 No. of theory]
2a-A-1 0 163'C 9g (The productis present as a OCH3 hemihydrate.) 2a-A-2 0 184'C 96 2a-A-3 0 ~ a OCH3 205'C 95 2a-A-4 0 ~ ~ 260'C 76 (After re-crystallisation from ethanol.) OH
2a-A-5 1 271'C 36 (The product is present as a hydrate (1.3 mol of H20 per OH mol of melamine).) 2a-A-6 0 ~ 288'C 39 (~~r re-~
OH crystallisation ~ from methanol.) Table 2b:
Comp. n R Melting point Yield [% of No. theory]
2b-A-1 0 ~ ~ OCH3 215C 97 Table 2c:
Comp. n R Melting Yield [% of theory]
No. point 70 (After recrystallisation from ethanol/watcr.
2c-A-1 0 200C The product is present as a hemihydratc.) OH
C1 ' 58 (After recrystallisation from ethanol/water.
2c-A-2 0 240C The productis present as a hydrate (0.75 mol of H20 per mol of OH melamine).) Example 6: Preparation of N-phenylmelamine (Compound 1-B-1 (=2-A-1)).
A mixture of 19.7 g (0.135 mol) of diaminochlorotriazine, 15.5 g (0.140 mol) of aniline, 1.3 ml of cone. hydrochloric acid (catalyst) is refluxed in 200 ml of water for 1 hour with stirring. The solution is filtered, and the filtrate is neutralised with cone.
sodium bicarbonate solution (pH = 7.2). The precipitate formed is filtered off with suction, washed until free of chloride and dried to constant weight. The product obtained has a melting point of 206°C. The yield is 86.4% of theory.
Example 7: Preparation of N-phen~ elamine hemihydrochloride (Comp_ound 1-B-2).
A mixture of 36.4 g (0.25 mol) of diaminochlorotriazine, 24.4 g (0.26 mol) of aniline and 7 ml of concentrated hydrochloric acid is refluxed in 500 ml of water for 1 hour. The solution is filtered, and the filtrate is cooled. The colourless crystals obtained are washed and dried to constant weight. The yield is 68.3% of theory. The product has a melting point of 259°C and is present as a dehydrate.
~~~~~:~~~
Example ~: The compounds in Table 3a to 3d are prepared in analogy to the process described in Example 6 or 7. The data given in Table 3a to 3d refer to the general formula given below.
IYHR
N N ~ (ilCl)n H2N ~ N ~ NH2 Table 3a:
Comp. n K Melting yield [lo of tltcoryJ
No. point ~- 65 (The product ~ ~ is present in 3a-B-1 0 210C the form of a hydrate (0.1 mol of H20 per mol of CH3 mclatninc).) / ~
3a-B-2 0 220C 88.2 (The product is present as a hydrate (0.2 mol of H20 CH3 per mol of melamine).) 3a-B-3 0 ~ ~ Chl 290C 83.8 (The product is present as 3 a hydrate (0.15 mol of H20 per mol of melamine).) / \
3a-B-4 0 C4H9- 161C 43 (After rccrystallisation from methanol.) 3a-B-5 0 ~ ~ 250C 76 C4H9_t 3a-B-6 0 ~ ~ 80C 81 (Addition of dimcthyl-acetamide. The product is S-C 16H33-n present as a sesquihydrate.) 75 (In the reaction, 3a-B-7 0 320C the free ~ ~ acid is also formed, (decomposition)which can be separated off by customary methods.
The COOCH3 product is present as a hydrate (U.2 mol of H20 per mol of melamine).) _z Table 3a continued:
Comp. n k Melting Yield [% of theory]
No. point 5g (After recrystallisation 3a-B-80 / \ 165C from acetic acid.
The product is pxescnt as a hydrate COOC2IIS (0.2 mol of 1I20 per mol of melamine).) 2g (Addition of dintethylacetamide.
3a-B-90 190C The product is present as a hydrate (0.1 mol of 1-I20 per COOC4H9-n of melamine).) /
3a-B-100 \ COOC4H ~-n 280C
/ \
64 (Prepared by trans-3a-B-110 152C
cstcrification of 3a-B-7 in COOC8H17-i the presence of Ti(OC~4H9)4.) *) 3a-B-120 / \ 65C 36.5 (Prepared by trans-esterification of 3a-B-8 in the presence of Ti(OC4H~)4.
COOC8H17-' Purified by recrystallisation from methylene chloride/
petroleum ether).
3a-B-130 ~ ~ 160C 43.8 (Addition of dimethyl-acetamide.) COOC1pH21-n 73.1 (After recrystallisation from water in the presence 3a-B-141 ~ 294C of activated carbon.
The product is present as a hydrate OH (0.8 mol of H20 per mol of melamine).) *) -C8H17-i- 2-ethylhexyl Table 3a continued:
Comp. n R Melting Yicld [3'0 of theory]
No. point 9 (~op~od from the 3a-B-150 242C .
hydrochloride with bicarbonate solution).
OH
73.8 (After recrystallisation ~ ~ from water in the 3a-B-161 OH 290C presence of activated carbon. The product is present as a monohydrate.) 3a-B-170 278C 49.3 (Addition of dimcthyl-acetamide. The product is present as a hemi-gH hydrate.) 89.8 3a-B-I80 203C
CI
85.0 3a-B-190 165C
87.9 ~
3a-B-200 Cl 23gC
~~C~~~~
Tabie 36:
Comp. n R Melting yield [~S'o of No. point thcoryl 36-B-1 0 ~ ~ 260C 78.2 (The product is present as _ a hydrate (1.2 mol of H2O
per mol of melamine).) 3b-B-2 0 / \ ~1C 76.8 (The product is present as a hydrate (0.15 mol of H20 per mol of melamine).) 3b-B-3 0 ~ ~ CH3 233C 87.0 (The product is present as a hydiate (0.15 mol of CH H20 per mol of 3 melamine).) gg,g (The product / \ is present as a 3b-B-4 0 CH3 260C hydrate (0.1 mol of H20 per mol of melamine).) CHg ~- 80 (The product is present as a 36-B-5 0 ~ ~ 277C hydrate (O.1S mol of H20 per mol of melamine).) CHg gg,5 (fhe product is present as a 3b-B-6 0 ~ ~ ~O.C hydrate (0.1 mol of H20 per mol of melamine).) CHg 3b-B-7 1 ~ ~ OCH3 26S'C 61.5 (bet recrystallisation from water in the presence of activated carbon.
The OCH~ product is present as a monohydrate.) 76.0 (After recrystallisation from water in the presence of 3b-B-8 1 256'C activated carbon.
The product is present as a OCH hydrate (0.2 mol of H20 per mol melamine).) Table 3b continued:
Comp. n R Mciting Yield [~% of thcory~
No. point OCH3 99.0 (Prepared by treating 3b-B-9 0 ~ ~ Ig6C 3b-B-g with bicarbonate solution.) OCH3 71.4 (After rccrystallisation 3b-B-10 1 ~ ~ 277C from water in dte presence of activated carbon.) OCH3 87.0 (Prepared by treating 3b-B-11 0 103C 3b-B-10 with bicarbonate / \ solution. This product is present as a monohydrate.) 79.5 (After recrystallisation 3b-B-12 1 OCH3 - from water in the presence of activated carbon.
The OCH3 product is present as a hydrate (0.2 mol of H20 per mol of melamine).) 99.4 (Prepared ~ ~ by treating 3b-B-13 0 OCH3 22SC 3b-B-12 with bicarbonate solution. The product is OCH3 present as a hydrate (0.2 mol of H20 per mol of melamine).) COOCH3 50 ('I7te product is present as a hemihydrate.) 3b-B-14 0 ~ ~ 267C
COOC8H17-i 51 (Prepared by Iransesterifi-cation of 36-$-14 in the 3b-B-15 0 ~ ~ g9C presence of Ti(OC4H9)4.
Purification by recrysLal-lisation from methylene COOCgHI7-i chloride/ether.) ~j .T ra J~ ~~
Table 3b continued Comp. n R Melting Yield [Wo of theory) No. point 85.0 (Addition / \ of dimcthyl-3b-B-160 Cl 245'C acetamide.The product is present as a hydrate C1 (0.25 mol of H20 per mol of melamine).) Cl 3b-B-170 / \ 80.1 (Addition 234'C of dimcthyl-aCCCamIdC).
Cl 86.2 (Addition ~ \ of dimcthyl-36-B-180 228C acetamide).
3b-B-190 / \ 229'C 85.5 (Addition of dimethyl-acetamide).
81.3 (Addition of dimethyl-3b-B-200 ~ ~ CI 201'C acetamide).
Table 3c:
Comp. n ~ Melting Yield [9'0 of theory]
No. point 3c-B-1 0 . ~ ~ O1~ 257C 61 (The product is present as a hydrate (0.7 mol of H20 per mol of melamine).) / \
3c-B-2 0 Crl3 255C ~ 80 (The Pr~uct is present as a hydrate (0.15 mol of H20 OH per mol of melamine).) 3c-B-3 0 ~ ~ CH3 232C 69.0 (The product is present as a hydrate (0.25 mol of H20 per mol of melamine).) OH
3c-B-4 0 ~ ~ OCH3 240C ~' 70 (The product is present as a hydrate (0.25 mol of OH
f120 per mol of melamine).) , \
3c-B-5 0 ~H3 262'C 75.2 (The product is present as a hydrate (0.1 mol of H20 CH per mol of melamine).) 3c-B-6 0 ~ ~ 268'C 89~ ~e Pr~uct is present as a hycfrate (0.15 mol of H20 per mol of melamine).) ~~~~~~'~
Table 3d:
Comp. n R Melting Yield [!o of No. point theory]
230C (ACter84.3 (The product purifi- is present 3d-B-1 0 OCH3 canon via as a hcmihydrate.
the hydro--~ chloride 210C.) 77,4 (Prepared by treating OCH3 3d-B-1 with HCl.
Recrystallisation from 3d-B-2 I ~ ~ 258C water in the presence of OCH3 activated carbon.
The product is present as a OCH3 hydrate (0.75 mol of H20 per mol of melamine).) 30.1 (Addition of dimethyl-3d-B-3 0 ~ ~ Cl 200C acetamide. Purifjcation by rcprecipitation using dimethyl sulfoxidc/I-I20).
CI .
22.1 (Addition of dimethyl-3d-B-4 0 Cl 150C acetamide. Purification by reprecipitation using dimethyl sulfoxide/H20).
Cl Cl i CI
91,7 (The productis / \ present 3d-B-5 0 OH > 300C as a hydrate (0.4 mol of H2U per mol of Cl melamine).) I
I
Example 9: A dry mixture comprising 100 parts of S-PVC (~Vinnol H 70 DF), 17 parts of dioctyl phthalate, 3 parts of epoxidised Soya bean oil, 0.33 part of zinc oleate, 0.53 part of barium p-(t-butyl)benzoate, 0.7 part of diisodecylphenyl phosphite, 0.44 part of ~SHELL
SOL A (aromatic hydrocarbon mixture) and 0.2 part of the melamine derivative listed in Tables 4a to 4h is rolled on mixing rolls at 190°C for 5 minutes. Test specimens of the 0.3 mm thick rolled sheet formed are subjected to thermal stress at 180°C in a test oven (~Mathi:; Thermotester). After the interval given, the: "yellowness index"
(YI) according to ASTM D 1925 is determined on a test specimen. The results are listed in Tables 4a to 4h.
Table 4a:
Mclamina YI
derivative after exposure time in minutes without 9.2 17.6 16.8 15.7 13.8 Compow~d 4.1 5.1 5.2 5.3 6.3 2a-A-4 Compowid 2.0 8.1 7.7 7.8 8.3 3a-B-14 Table 4b:
Melamine YI
derivative after exposure time in minutes without 10.4 14.4 15.4 16.6 16.8 Compow~d 5.5 6.7 6.6 7.7 9.0 Table 4c:
Melamin~: YI
derivative after exposure time in minutes without 9.7 12.3 14.6 16.3 17.0 Compowtd 5.7 7.7 7.9 7.7 8.2 3a-B-18 Compowtd SS 6S 6.5 7.0 7.4 3a-B-19 Compowtd 3a-B-20 5.3 6.0 6.5 7.0 7.3 ~~~~~Y~z -2f>-Table 4d:
Melamine YI
derivative after exposure time in minutes without 9.8 12.0 13.5 15.8 17.1 Compound 5.7 6.4 7.4 7.5 7.8 ~
3a-B-1 Compound 5.4 6.5 6.7 7.0 7.3 3a-B-2 Compound 3a-B-3 5.3 7.0 7.5 7.4 7.6 Compound 3a-B-4 5.2 6.3 6.6 7.0 7.0 Compound 3a-B-5 5.6 7.3 7.3 7.6 8.3 Table 4e:
Melamine n derivative after exposure time in minutes IS
without 9.0 14.8 16.7 17.4 17.1 Compound 3,3 4.5 5.0 5.5 6.5 3b-B-1 Compound 3.2 4.8 4.7 5.1 5.6 3b-B-2 Compound 3b-B-3 2.9 4.4 5.0 5.2 5.8 Compound 3b-B-4 3.3 3.6 4.2 4.6 5.5 Compound 3b-B-5 2.7 3.5 3.7 4.7 4.9 Table 4f:
Melamine YI
derivative after exposure time in minutes without 8.4 13.8 15.0 16.3 16.5 Compound 3.0 4.4 4.6 4.9 5.9 Table 4g:
Melamine YI
derivative after exposure time in minutes without 8.3 13.7 15.1 17.6 17.9 Compound 3.1 4.3 4.6 5.0 5.8 3a-B-8 Compound 3.p 5.1 6.0 6.1 6.3 3 a-B-10 Compotmd 4.3 5.2 5.7 6.6 7 3a-B-II .
Compound 3.8 5.6 6.2 6.7 8 3b-B-l.i .
Compotmd 4.3 5.7 5.9 7.1 7.6 3b-B-15 Table 4h:
Melamine YI
derivative after exposure time in minutes without 10,7 16.4 18.3 17.9 17.9 Compound 3.5 4.8 5.2 5.9 6.4 3b-B-2') Compound 3.1 4.2 5.0 5.2 6.1 3b-B-6 ~~~~~'~~
Example 10: A dry mixture comprising 100 parts of P'VC ( ~2 Solvic 2~4 GA), 3 parts of epoxidised Soya bean oil, 0.35 part of calcium stearate, 0.15 part of zinc stearate, 0.55 part of diisodecylphenyl phosphite, and 0.3 part of the melamine derivative listed in Tables Sa to 5k is rolled on mixing rolls at 180°C for 5 minutes. Test specimens of the 0.3 mm thick rolled sheet formed are subjected to thermal stress at 180°C in a test oven (~Mathis Thermotester). After the interval given, the "yellowness index" (YI) according to ASTM
D 1925 is determined on a test specimen. The results are listed in Tables 5a to 5k.
Table Sa:
Yl after exposure time in minutes Melamine derivative IS
without 20.1 25.1 29.9 31.8 28.1 31.6 62.8 Compound 2a-A-3 2.6 4.7 4.0 6.9 10.5 18.7 35.7 Table Sb:
Melamine YI
derivative after exposure time in minutes S
without 19.5 27.6 30.5 33.4 30.2 I
Compound 3.4 4.9 5.9 7.6 12.8 Table 5c:
Melamine YI
derivative after exposure time in minutes I
S
without 22.4 37.4 38.5 36.9 41.2 Compound 2.7 7.1 10.3 14.7 24.5 3a-B-19 Compound 3.2 8.3 10.6 15.0 24.7 3a-B-20 ~
~~3~~'~2 Table Sd:
Melamine n derivative after exposure time in minutes without 1G.9 36.6 36.4 34.9 53.3 Compotutd 36-B-5 2.5 10.4 12.8 16.6 26.6 Table Se:
Melamine n derivative after exposure time in minutes without 17.5 36.2 36.8 345 33.3 Compound 3d-B-1 1.9 4.8 6.8 10.0 15.8 Table Sf:
Melamine n derivative after exposure time in minutes IS
without 18.0 38.3 38.5 34.7 37.0 Compottrtd 2c-A-1 3.6 6.1 8.8 13.3 18.2 Table SQ:
Melamine YI
derivative after exposure time in minutes IS
without 16.3 37.8 38.2 34.2 44.7 Compotutd 3a-B-12 2.8 7.0 9.4 14.0 23.7 Table Sh:
Melamine YI
derivative after exposure time in minutes without . 17.5 36.3 37.4 57.2 79.0 Compotutd 2a-All 3.2 9.2 11.8 16.6 21.8 Compound 3 a-B-15 3.1 I 1.1 13.1 17.6 24.
I
Table Si:
Melamim: YI
derivative after exposure time in minutes without 15.7 36.2 37.3 49.3 74.0 Compotutd 3a-B-13 6.2 11.4 12.6 15.6 20.6 Table Si:
Melamine YI
derivative after exposure time in minutes without 17.0 38.4 37.5 33.8 44.5 Compound 36-B-11 .2.1 6.6 8.5 10.6 12.8 t I t Table Sk:
Melamine YI
derivative after exposure time in minutes without 15.0 32.1 37.7 36.9 31.8 Compotmd 3b-B-20 1.5 5.0 5.7 7.4 11.9 Example 11: A dry mixture comprising 100 parts of S-PVC (~Vinnol H 70 DF), 17 parts of dioctyl phthalate, 3 parts of epoxidised soya bean oil, 0.33 part of zinc oleate, 0.53 part of barium p-(t-butyl)benzoate, 0.7 part of diisodecylphenyl phosphite, 0.44 part of butyldiglycol and 0.2 part of the melamine derivative listed in Table 6 is rolled on mixing rolls at 190°C for 5 minutes. Test specimens of the 0.3 mm thick rolled sheet formed are subjected to thermal stress at 180°C in a test oven (~Mathis Thermotester). After the interval given, the "yellowness index" (YI) according to ASTM D 1925 is determined on a test specimen. The results are listed in Table 6.
Table 6:
Melamine derivativeYI
after exposure time in minutes without 9.211.613.615.2 18.518.7 17.415.9 14.6 15.1 Compound 2a-A-3 2.83.0 3.2 3.7 3.8 4.3 5.2 5.1 5.5 7.7
Examples of R as C3-C2oalkenyl are allyl, 2-methallyl, 3-methylbut-2-enyl, 3-methylbut-3-enyl, hexenyl, decenyl, undecenyl, heptadecenyl or oleyl.
Preferred meaning~~ are allyl, methallyl and oleyl.
Examples of R as C3-CBCycloalkyl which is unsubstituted or substituted by Ct-C4alkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 4-butylcyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. CS-C~cycloalkyl, in particular cyclohexyl, is preferred.
R as C~-(a tphenylalkyl is, for example, benzyl or phenylethyl.
Example., of R as C~-Citphenylalkyl which is substituted by 1 to 3 radicals according to the definition are o-, m- or p-chlorobenzyl, 2,3-dichlorobenzyl, 2,4-dichlorobenzyl, 2,5-dichlorobenzyl, 2,6-dichlorobenzyl, 3,4-dichlorobenzyl, 2,4,5-trichlorobenzyl, 2,4,6-trichlorobenzyl, o-, m- or p-hydroxybenzyl, o-, m- or p-methylbenzyl, 2,3-dimethylbenzyl, 2,4-dimethylbenzyl, 2,5-dimethylbenzyl, 2,6-dimethylbenzyl, 3,4-dimethylbenzyl, 3,5-dimethylbenzyl, 2-methyl-4-tart-butylbenzyl, 2-ethylbenzyl, 2,6-diethylbenzyl, 2,6-diethyl-4-methylbenzyl, 2,6-diisopropylbenzyl, 4-tent-butylbenzyl, 2-chloro-6-methylbenzyl, 3-chloro-2-methylbenzyl, 3-chloro-4-methylbenzyl, 4-chloro-2-methylbenzyl, 5-chloro-2-methylbenzyl, 2,6-dichloro-3-methylbenzyl, 2-hydroxy-4-methylbenzyl, 3-hydroxy-4-methylbenzyl, o-, m- or p-methoxybenzyl, o-, m-or p-ethoxybenzyl, 2,4-dimethoxybenzyl, 2,5-dimethoxybenzyl, 2,5-diethoxybenzyl, 2-methoxy-5-methylbenzyl, 4-methoxy-2-methylbenzyl, 3-chloro-4-methoxybenzyl, 3-chloro-6-methoxybenzyl, 3-chloro-4,6-dimethoxybenzyl or 4-chloro-2,5-dimethoxybenzyl.
Examples of Rt, R2 and R3 as Ct-C2oalkyl are, in addition to the meanings given above for R = alkyl, methyl, ethyl, propyl, isopropyl, butyl, ten-butyl, pentyl, hexyl and heptyl.
Examples of X, Rt, R2 and R3 as Ct-CZOalkyloxy are methoxy, ethoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, tridecyloxy, hexadecyloxy or octadecyloxy. One of the preferred meanings for Rt, RZ and R3 is Ct-C4alkyloxy, in particular methoxy and ethoxy.
Examples of X, Rt, RZ and R3 as Ct-C2oalkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, dodecylthio, tridecylthio, hexadecylthio or octadecylthio. C8-CtBalkylthio is preferred.
Examples of Rt, RZ and R3 as C2-Ct2alkyloxycarbonyl are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, octyloxp:arbonyl and decyloxycarbonyl.
Examples of Rt, R2 and R3 as C2-Ct2alkanoyl are acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl or decanoyl.
Example: of group IIb are o-, m- or p-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 3,4-dichlorophenyl, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl, o-, m- or p-hydroxyphenyl, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-4-ten-butylphenyl, 2-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl, 3,5-diethylphenyl, 2,6-diethyl-4-methylphenyl, 2,6-diisopropylphenyl, 4-tent-butylphenyl, 3,5-di-tett-butylphenyl, 2-chloro-6-methylphenyl, 3-chloro-2-methylphenyl, 3-chloro-4-methylphenyl, 4-chloro-2-methylphenyl, 5-chloro-2-methylphenyl, 2,6-dichlaro-3-methylphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m-or p-propoxyphenyl, o-, m- or p-butoxyphenyl, o-, m- or p-hexyloxyphenyl, o-, m- or p-octyloxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,5-diethoxyphenyl, 2-methor:y-5-methylphenyl, 4-methoxy-2-methylphenyl, 3-ehloro-4-methoxyphenyl, 3-chloro-6-methoxyphenyl, 3-chloro-4,6-dimethoxyphenyl, 4-chloro-2,5-dimethoxyphenyl, o-, m- or p-methylthiophenyl, o-, m- or p-ethylthiophenyl, o-, m- or p-propylthiophenyl, o-, m- or p-butylthiophenyl, o-, m- or p-pentylthiophenyl, o-, m- or p-hexylthiophenyl, o-, m- or p-heptylthiaphenyl, o-, m- or p-octylthiophenyl, o-, m-or p-nonylthiophenyl, o-, m- or p-decylthiophenyl, o-, m- or p-phenylphenyl and 2-hydroxy-4-methylphenyl, 3-hydroxy-4-rnethylphenyl and a group of the formula ct-c4-alkyl / \ oft C t-C4-alkyl Preferred meanings for group IIb can be seen from Examples 1 to g given below.
In the group of the formula IIb, R1 and/or R2 are particularly prefererably hydrogen.
Compositions which are of interest are those in which R is Cto-Ctg-alkyl, OH-substituted Cl-Cloallcyl, C3-Ctoalkenyl, CS-C~cycloalkyl, Ct-C4alkyl-substituted Cg-C~cycloalkyl, benzyl, benzyl which is substituted on the phenyl by 1 to 3 radicals, these radicals, independently of one another, being hydroxyl, chlorine, Ct-C4alkyl, methoxy or ethoxy, or R is furthermore a group of the formula lIa or IIb, in which X is Ct-Ctoalkyloxy, Cg-CtBalkylthio, phenyloxy, phenylthio, benzyloxy or benzylthio and Rt, R2 and R3, independently of one another, are hydrogen, Ct-Ctoalkyl, Ct-Ctoalkyloxy, Cg-CtBalkylthio, C2-Ct2alkyloxycarbonyl, C2-C6alkanoyl, phenyloxy, phenylthio, hydroxyl, mercapto or chlorine.
Compositions in which R is Cto-Ctgalkyl, OH-substituted Ct-C6alkyl, allyl, cyclohexyl or benzyl are also of interest.
R is preferably the group lIb.
Preference is also given to compositions in which R is a group of the formula IIb and the radicals Rt, R2 and R3, independently of one another, are hydrogen, Ct-C4alkyl, Ct-C4alkyloxy, Cg-Ct6alkylthio, C2-Ct2alkyloxycarbonyl, hydroxyl, mercapto or chlorine.
Particulw preference is given to compositians in which R is a group of the formula IIb, RI
is hydrogen, R2 and Rg, independently of one another, are Cl-C4alkyl, Ci-C4a(kyloxy, Cg-Ctbalkylthio, C2-Ct2alkyloxycarbonyl, hydroxyl or chlorine and RZ is additionally hydrogen.
Compositions which are of particular interest are those in which R is a group of the formula IIb, Rt and R2 are hydrogen and R3 is CI-C4alkyl, Ct-C4alkyloxy, Cg-Ctbalkylthio, C2-CF2alkyloxycarbonyl, hydroxyl or chlorine, in particular CF-C4alkyloxy or hydroxyl.
According to a further preference, component b) can be present as hydrochloride.
Componc;nt c) is preferably an Me(II) carboxylate, in which Me(II) is Ba, Ca, Mg, Cd or Zn. The c:arboxylates are preferably salts of carboxylic acids having 7 to 20 C atoms, for example benzoates, alkanoates or alkenoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or 2-ethylhexanoates. Stearates, oleates or p-tert-bmylbenzoates are particularly preferred.
Mixtures of Ba/Zn or CalLn carboxylates are also particularly preferred as component c).
An Me(Il) phenolate as component c) is in particular a C~-CZp(o-, m- or p-)alkylphenolate, for example o-, m- or p-nonylphenolate.
According to a further preference, the compositions according to the invention contain an epoxy compound and/or a phosphite as additional component d).
The epoxy compound is preferably an epoxidised oil or an epoxidised fatty acid ester, for example epoxidised soya bean oil, epoxidised butyl oleate and epoxidised octyl oleate.
The phosphites are preferably those of the formula Al0 O O Al0 CH3 \ / \ \ t A20-P, Al0-P P-OAZ, P-OCH2CH O, P-OCH2CHOCHCH2 , \ / / ~ i i A30 O O A30 2 OAt CH3 CH3 n in which A1, A2 and A3, independently of one another, are C4-Ctgalkyl, C6-Ctgalkenyl, CS-C~cycloalkyl, phenyl or phenyl which is substituted by one to three Ct-Ct2alkyl groups.
Examples are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite. Preference is given to the aryl _7_ dialkyl and the alkyl diaryl phosphates, for example phenyl didecyl, (2,4-di-ten-butylphenyl) didodecyl, (2,6-di-tcrt-butylphenyl) didodecyl phosphate and the dialkyl and diaryl pentacrythritol diphosphitcs, for example distearyl pentaerythritol diphosphite. Preference is also given to the tetrapheny:l and tetraalkyl [1,2-dipropylene glycol] diphosphites and the poly[1,2-dipropylene glycol phenyl phosphates]
and the poly[1,2-dipropylene glycol alkyl phosphates].
Particularly preferred organic phosphates are distearyl pentaerythritol diphosphite, tris(nonylphenyl)phosphite, phenyldidccylphosphite, tetraphenyl [1,2-dipropylene glycol]
diphosphite and poly[1,2-dipropylene glycol phenyl phosphate].
The Me(II) carboxylates or phenolates are preferably used in amounts of 0.05 to 5% by weight.
The phosphates are used, for example, in concentrations of 0.3 to 5, preferably 0.5 to 1, by weight, and the epoxy compounds, for example epoxidised soya bean oil, advantageously in concentrations of 1 to 8, preferably 1 to 3, % by weight.
The compounds of the formula I are preferably incorporated in the chlorine-containing polymer in amounts of 0.05 to 1 or 0.01 to 0.9, in particular 0.1 to 0.7, % by weight.
The % by weight given refers in each case to the material to be stabilised.
The chlorine-containing polymers are preferably vinyl chloride homopolymers or copolymers. Examples of suitable comonomers for the copolymers are: vinyl acetate, vinylidene chloride, trans-dichloroethene, ethylene, propylene, butylene, malefic acid, acrylic acid, fumaric acid, itaconic acid. Further suitable chlorine-containing polymers are postchlorinated PVC and chlorinated polyolefins, furthermore graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of the abovementioned homo-and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, in particular with ABS, MBS, NBR, SAN, EVA.
Further preference is given to suspension and bulk polymers and to emulsion polymers.
Polyvinyl chloride is particularly preferred as chlorine-containing polymer.
_g_ The invention further relates to the use of a stabiliser system containing components b) and c) for stabilising a chlorine-containing polymer against thermodegradation.
Depending on the intended use of the polymers, further additives can be incorporated before or during the incorporation of the stabilisers, for example phenolic antioxidants, lubricants (preferably montan waxes or glycerol esters, fatty acid esters, paraffins, amide waxes, stear-ic acid, mono- and dihydroxystearic acid, higher fatty alcohols), plasticisers, fillers, carbon black, asbestos, kaolin, talc, glass fibres, modifiers, (impact-resistant additives), processing aids (for example polymethacrylic esters), fluorescent whitening agents, pigments, light stabilisers, ster-ically hindered amines, UV
absorbers, flame retardant;> or antistatics.
Further possible additives are furthermore f3-aminocrotonates, for example the compounds described in DE-A 804,442, DE-A 807,207 and JP-A 75/17,454, pyrroles, for example the compounds mentioned in EP-A 22,087, aminouracils, for example the compounds disclosed in EP-A 65,934, aminothiouracils, for example the compounds known from EP-A 41,479, polyols, for example the compounds described in DE-A 3,019,910, f3-diketones, for example the compounds mentioned in DE-A 2,600,516, hydrotalcites, in particular the compounds described in DE-A 3,843,581, or also mixtures of f3-diketones and hydrotalcites, as described in EP-A 63,180, furthermore Mg/Al carbonates, for example the Mg/Al carbonates disclosed in JP-A-Sho 62/267,347 (=Chemical Abstracts 108:168 635 h), and Alcamizers, for example 4 Mg0 A1203.C02.9 H20, 4 Mg0 Ai2O3.C02.6 H20, Zn0 3MgU A1203.C02.8-9 H20, Zn0 3 Mg0 A1203.C02.5-6 H20 and Mg4A12(t~H)12(C03)t-Xn(C104)xmH20.
Possible additives are also chemical blowing agents for expanded rigid or plasticised polyvinyl chloride, for example NaHC03 and the blowing agents mentioned in "Gachter,~iVliiller; Taschenbuch der Kunststoff-Additive (Handbook of plastic additives), Carl Hanser Verlag Munich-Vienna, 2nd edition, 1983" on page 651.
The stabiliser components are most favourably incorporated in the chlorine-containing polymer, as is usual, on mixed rolls, for example in a 2-roll mill at temperatures between 150° and 200°C. In general, sufficient homogenisation can be obtained within 5 to 1S
minutes. The components can be added individually or together as a premixture.
A liquid premixture has proven to be advantageous, i.e, the homogenisation is carried out in the presence of inert solvents and/or plasticisers.
~~.~~~~' The compositions according to the invention can be processed to give moulded articles by the moulding processes customary for this, for example by extrusion, injection-moulding or calandering. The use of plastisols is also possible.
The compositions according to the invention are preferably used for the manufacture of electro cables, hollow articles, for example pipes, and in particular sheets in the automobile industry. This use is also provided by the invention. A
particularly preferred area of application is the manufacture of sheets for the interior of automobiles, in particulw for those as described in DE-A 3,227,107 and DE-A 3,401,482.
The compositions according to the invention are particularly advantageously used for the manufacture of deep-drawing sheets and flexible sheets based on PVC, in particular for the use in the automobile industry.
The compounds of the formula I can be prepared in analogy to known processes.
Preparation processes are described, for example, in the following publications: D.F.
Walker et al.; J. Am. Pharm. Assoc. 39, 393 (1950), D.W. Kaiser et al.; J. Am.
Chem. Soc.
73, 2984 ( 1951 ), A.B. Borkovec et al.; J. Med. Chem. 10, 457 ( 1967). ' When R has one of the abovementioned meanings other than the group IIb, it is advantageous to prepare the melamine derivatives by the following scheme:
Scheme ~~
Cl i N N base N N
+ RNH~ ---~ ~ + HC1 H2N Y NH2 H2N \N NH2 In general, water is a suitable reaction medium. In some cases, in particular if R is a long-chain allcyl radical, it is advantageous to add a solubiliser, for example dirnethyhicetamide. The base is, for example, alkali metal hydroxide, preferably sodium hydroxid.~.
The melamine obtained can be converted to the corresponding hydrochloride by heating it ~~~ta~~
with concentrated hydrochloric acid (slight excess). Inversely, it is possible to obtain again the melamine from the hydrochloride by treating with, for example, alkali metal hydroxide or alkali metal bicarbonate solution, which would constitute a further purification step.
In some eases, it is also possible to prepare compounds of the formula I in which R is a group of the formula IIb by the above scheme A; however, in these cases, the basicity of the amine; must be higher.
Compounds of the formula I in which R is a group of the formula IIb are preferably prepared by Scheme B given below.
Scheme 13:
Cl NHR
N /~ N HCl N ~ N
+ RNH2 ----~ ~ HCl In this case, too, water is a suitable reaction medium, it being possible, if required, to add again a solubiliser. The hydrochloride is advantageously converted into the corresponding melamine; derivative as described above.
In general, the compounds of the formula I and their hydrochlorides have a defined hydrated water content.
The starting materials are commercially available or can be prepared in analogy to processes known to one skilled in the art. The preparation of diaminochlorotriazine is described, for example, by J.T. Thurston et al. in "J. Am. Chem. Soc. 73, 2981 (1951)".
The compounds of the formula I can also be used against photolytic degradation of chlorine-containing polymers.
The invention also relates to the novel compounds of the formula Ia and hydrochlorides thereof, NIiR
N i 'N
(la) HZN \N NHZ
in which R is C~-Cttphenylalkyl which is substituted on the phenyl by 1 to 3 radicals, the radicals, independently of one another, being hydroxyl, chlorine, Ct-C4alkyl, methoxy or ethoxy, or R is furthermore a group of the formula lIa, II-b-1, II-b-2 or II-b-3, Y1 . ~ Y4.
- CH2- CH- CH2-X , I
Y3 1'6 Y9 (IIa) (II-b-1) (II-b-2) (II-b-3) in which X is Cl-C2oalkyloxy, Ct-C2oalkylthio, phenyloxy, phenylthio, benzyloxy or benzylthio, Yt, Y2 and Y3, independently of one another, are Ct-Czoalkylthio, C2-Ct2allcyloxycarbonyl or mercapto, and Yt and Y2 are additionally hydrogen, Y4 is methoxy, ethoxy or hydroxyl, YS and Y6, independently of one another are Ct-C2palkyl, Ct-C2palkyloxy, Cl-CZpalkylthio, C2-Ct2alkyloxycarbonyl, C2-Ct2alkanoyl, phenyl, phenyloxy, phenylthio, hydroxyl, mercapto or chlorine, and YS is additionally hydrogen, Y~, Yg and Y9, independently of one another, are C2-C2ealkyl or C2-Ct2alkyloxycarbonyl and Yg is additionally hydrogen.
For the compounds of the formula Ia, the same preferences apply as for the compounds of the formula I, and the radicals Yt to Y9 correspond to the radicals Rt to R3.
The examples which follow illustrate the invention in more detail. Parts and percentages are by weight, unless stated otherwise.
Example 1: Preparation of N-(n-dodecyl)melamine (Com_pound 1-A-1).
A mixture of 14.6 g (0.1 mol) of diaminochlorotriazine, 19.5 g (0.105 mol) of n-dodecylamine and 4.0 g (0.1 mol) of sodium hydroxide in 200 ml of water is refluxed for 5 hours. The solid formed is filtered off with suction, washed until free of chloride and then treated with a mixture of methylene chloride/ether (1:1). The precipitate is filtered off and boiled in dimethylformamide. After filtration, the concentrated filtrate is poured into ~, 5'~ F~ (''~ f ~~e~c.7~
water with stirring. The precipitate formed is dried to constant weight. The yield is 65% of theory. The product contains 0.1 mol of hydrated water per mole of melamine and melts at 119°C.
Example 2: The compounds in Table 1 are prepared in analogy to the process described in Example 1.
Table l:
NHR
N i 'N
H2N~N- _NH2 Compound No. R Melting Yield [% of theory]
point 1-A-2 -(CH2)3-OH160C 87 1-A-3 -(CH2)5-OH- -1-A-4 -CH2-CH=CH2172C 57.2 (The product is present in the form of a hydrate (0.25 mol of H20 per mol of melamine).
66 (After recrystallisation from acetic acid. The product is present in the 1-A-$ ~ 146 C
form of a hydrate (0.6 mol of F120 per mol of melamine).) i ~ i i 2J P~ ~ r9 Example 3: Preyaration of N-benzylmelamine ~drochloride (Com-pound 1-A-7) 10.8 g (0.05 mol) of compound 1-A-6 are refluxed tol;ether with 6.84 g (0.06 mol) of 32%
hydrochloric acid for 1 hour with stirring. The clear solution is Gaoled to 0°C, and the crystals formed are filtered off, washed and dried. The yield is 73.8% of theory. The product has a melting point of 275°C.
Example 3a: Preparation of N-f3-(2'-ethylhexyl)oxy-2-hydroxypropyllmelami_ne Com ound 1A-8).
A mixture of 29.1 g (0.2 mol) of diaminochlorocriazine, 40.7 g (0.2 mol) of 3-(2'-ethylhexyl)oxy-2-hydroxypropylamine and 300 ml of water is refluxed. 0.2 mol of NaOH in 80 ml of water are added dropwise over a period of 1 hour. The reaction mixture is then refluxed for 2 hours. 25 ml of concentrated hydrochloric acid are added to the resulting oil, giving a clear solution. Upon cooling, the hydrochloride of N-[3-(2'-ethylhexyl)oxy-2-hydroxypropyl]melamine precipitates and is ehen neutralised with NaFIC03 at 40°C. The wax-like product obtained is washed until free of chloride with ice water and dried in vacuo. The yield is 86.6% of theory. The product has a melting point of 1.09 - 115°C.
Example 3b: Preparation of N-n-hexylmelamine (Compound 1-A-9).
The prep;~ration is carried out in analogy to Example 3a. The yield is 70.8%
of theory. The product has a melting point of 116-119°C.
Example 4: Preparation of N-phenylmelamine (= Compound 2-A-1) A mixture of 14.6 g (0.1 mol) of diaminochlorotriazine, 9.8 g (0.105 mol) of aniline and 4.0 g (0.1 mol) of sodium hydroxide in 30 ml of water is refluxed for 2 hours with the addition of 200 ml of water. The cloudy solution is cooled, the precipitated solid is filtered off, washed until free of chloride and dried to constant weight. The product obtained is purified by dissolving it in glacial acetic acid and then treating it with bicarbonate. The yield is 62% of theory. The product has a melting point of 202°C.
Example 5: The compounds listed in Tables 2a to 2c are prepared in analogy to the process described in Example 4. The data given in Tables 2a to 2c refer to the general formula liven below.
ih!
NHR
N i 'N . (HCI)n H2N ~ N ~ NH2 Table 2a;
Comp. n R Melting point Yield [3'0 No. of theory]
2a-A-1 0 163'C 9g (The productis present as a OCH3 hemihydrate.) 2a-A-2 0 184'C 96 2a-A-3 0 ~ a OCH3 205'C 95 2a-A-4 0 ~ ~ 260'C 76 (After re-crystallisation from ethanol.) OH
2a-A-5 1 271'C 36 (The product is present as a hydrate (1.3 mol of H20 per OH mol of melamine).) 2a-A-6 0 ~ 288'C 39 (~~r re-~
OH crystallisation ~ from methanol.) Table 2b:
Comp. n R Melting point Yield [% of No. theory]
2b-A-1 0 ~ ~ OCH3 215C 97 Table 2c:
Comp. n R Melting Yield [% of theory]
No. point 70 (After recrystallisation from ethanol/watcr.
2c-A-1 0 200C The product is present as a hemihydratc.) OH
C1 ' 58 (After recrystallisation from ethanol/water.
2c-A-2 0 240C The productis present as a hydrate (0.75 mol of H20 per mol of OH melamine).) Example 6: Preparation of N-phenylmelamine (Compound 1-B-1 (=2-A-1)).
A mixture of 19.7 g (0.135 mol) of diaminochlorotriazine, 15.5 g (0.140 mol) of aniline, 1.3 ml of cone. hydrochloric acid (catalyst) is refluxed in 200 ml of water for 1 hour with stirring. The solution is filtered, and the filtrate is neutralised with cone.
sodium bicarbonate solution (pH = 7.2). The precipitate formed is filtered off with suction, washed until free of chloride and dried to constant weight. The product obtained has a melting point of 206°C. The yield is 86.4% of theory.
Example 7: Preparation of N-phen~ elamine hemihydrochloride (Comp_ound 1-B-2).
A mixture of 36.4 g (0.25 mol) of diaminochlorotriazine, 24.4 g (0.26 mol) of aniline and 7 ml of concentrated hydrochloric acid is refluxed in 500 ml of water for 1 hour. The solution is filtered, and the filtrate is cooled. The colourless crystals obtained are washed and dried to constant weight. The yield is 68.3% of theory. The product has a melting point of 259°C and is present as a dehydrate.
~~~~~:~~~
Example ~: The compounds in Table 3a to 3d are prepared in analogy to the process described in Example 6 or 7. The data given in Table 3a to 3d refer to the general formula given below.
IYHR
N N ~ (ilCl)n H2N ~ N ~ NH2 Table 3a:
Comp. n K Melting yield [lo of tltcoryJ
No. point ~- 65 (The product ~ ~ is present in 3a-B-1 0 210C the form of a hydrate (0.1 mol of H20 per mol of CH3 mclatninc).) / ~
3a-B-2 0 220C 88.2 (The product is present as a hydrate (0.2 mol of H20 CH3 per mol of melamine).) 3a-B-3 0 ~ ~ Chl 290C 83.8 (The product is present as 3 a hydrate (0.15 mol of H20 per mol of melamine).) / \
3a-B-4 0 C4H9- 161C 43 (After rccrystallisation from methanol.) 3a-B-5 0 ~ ~ 250C 76 C4H9_t 3a-B-6 0 ~ ~ 80C 81 (Addition of dimcthyl-acetamide. The product is S-C 16H33-n present as a sesquihydrate.) 75 (In the reaction, 3a-B-7 0 320C the free ~ ~ acid is also formed, (decomposition)which can be separated off by customary methods.
The COOCH3 product is present as a hydrate (U.2 mol of H20 per mol of melamine).) _z Table 3a continued:
Comp. n k Melting Yield [% of theory]
No. point 5g (After recrystallisation 3a-B-80 / \ 165C from acetic acid.
The product is pxescnt as a hydrate COOC2IIS (0.2 mol of 1I20 per mol of melamine).) 2g (Addition of dintethylacetamide.
3a-B-90 190C The product is present as a hydrate (0.1 mol of 1-I20 per COOC4H9-n of melamine).) /
3a-B-100 \ COOC4H ~-n 280C
/ \
64 (Prepared by trans-3a-B-110 152C
cstcrification of 3a-B-7 in COOC8H17-i the presence of Ti(OC~4H9)4.) *) 3a-B-120 / \ 65C 36.5 (Prepared by trans-esterification of 3a-B-8 in the presence of Ti(OC4H~)4.
COOC8H17-' Purified by recrystallisation from methylene chloride/
petroleum ether).
3a-B-130 ~ ~ 160C 43.8 (Addition of dimethyl-acetamide.) COOC1pH21-n 73.1 (After recrystallisation from water in the presence 3a-B-141 ~ 294C of activated carbon.
The product is present as a hydrate OH (0.8 mol of H20 per mol of melamine).) *) -C8H17-i- 2-ethylhexyl Table 3a continued:
Comp. n R Melting Yicld [3'0 of theory]
No. point 9 (~op~od from the 3a-B-150 242C .
hydrochloride with bicarbonate solution).
OH
73.8 (After recrystallisation ~ ~ from water in the 3a-B-161 OH 290C presence of activated carbon. The product is present as a monohydrate.) 3a-B-170 278C 49.3 (Addition of dimcthyl-acetamide. The product is present as a hemi-gH hydrate.) 89.8 3a-B-I80 203C
CI
85.0 3a-B-190 165C
87.9 ~
3a-B-200 Cl 23gC
~~C~~~~
Tabie 36:
Comp. n R Melting yield [~S'o of No. point thcoryl 36-B-1 0 ~ ~ 260C 78.2 (The product is present as _ a hydrate (1.2 mol of H2O
per mol of melamine).) 3b-B-2 0 / \ ~1C 76.8 (The product is present as a hydrate (0.15 mol of H20 per mol of melamine).) 3b-B-3 0 ~ ~ CH3 233C 87.0 (The product is present as a hydiate (0.15 mol of CH H20 per mol of 3 melamine).) gg,g (The product / \ is present as a 3b-B-4 0 CH3 260C hydrate (0.1 mol of H20 per mol of melamine).) CHg ~- 80 (The product is present as a 36-B-5 0 ~ ~ 277C hydrate (O.1S mol of H20 per mol of melamine).) CHg gg,5 (fhe product is present as a 3b-B-6 0 ~ ~ ~O.C hydrate (0.1 mol of H20 per mol of melamine).) CHg 3b-B-7 1 ~ ~ OCH3 26S'C 61.5 (bet recrystallisation from water in the presence of activated carbon.
The OCH~ product is present as a monohydrate.) 76.0 (After recrystallisation from water in the presence of 3b-B-8 1 256'C activated carbon.
The product is present as a OCH hydrate (0.2 mol of H20 per mol melamine).) Table 3b continued:
Comp. n R Mciting Yield [~% of thcory~
No. point OCH3 99.0 (Prepared by treating 3b-B-9 0 ~ ~ Ig6C 3b-B-g with bicarbonate solution.) OCH3 71.4 (After rccrystallisation 3b-B-10 1 ~ ~ 277C from water in dte presence of activated carbon.) OCH3 87.0 (Prepared by treating 3b-B-11 0 103C 3b-B-10 with bicarbonate / \ solution. This product is present as a monohydrate.) 79.5 (After recrystallisation 3b-B-12 1 OCH3 - from water in the presence of activated carbon.
The OCH3 product is present as a hydrate (0.2 mol of H20 per mol of melamine).) 99.4 (Prepared ~ ~ by treating 3b-B-13 0 OCH3 22SC 3b-B-12 with bicarbonate solution. The product is OCH3 present as a hydrate (0.2 mol of H20 per mol of melamine).) COOCH3 50 ('I7te product is present as a hemihydrate.) 3b-B-14 0 ~ ~ 267C
COOC8H17-i 51 (Prepared by Iransesterifi-cation of 36-$-14 in the 3b-B-15 0 ~ ~ g9C presence of Ti(OC4H9)4.
Purification by recrysLal-lisation from methylene COOCgHI7-i chloride/ether.) ~j .T ra J~ ~~
Table 3b continued Comp. n R Melting Yield [Wo of theory) No. point 85.0 (Addition / \ of dimcthyl-3b-B-160 Cl 245'C acetamide.The product is present as a hydrate C1 (0.25 mol of H20 per mol of melamine).) Cl 3b-B-170 / \ 80.1 (Addition 234'C of dimcthyl-aCCCamIdC).
Cl 86.2 (Addition ~ \ of dimcthyl-36-B-180 228C acetamide).
3b-B-190 / \ 229'C 85.5 (Addition of dimethyl-acetamide).
81.3 (Addition of dimethyl-3b-B-200 ~ ~ CI 201'C acetamide).
Table 3c:
Comp. n ~ Melting Yield [9'0 of theory]
No. point 3c-B-1 0 . ~ ~ O1~ 257C 61 (The product is present as a hydrate (0.7 mol of H20 per mol of melamine).) / \
3c-B-2 0 Crl3 255C ~ 80 (The Pr~uct is present as a hydrate (0.15 mol of H20 OH per mol of melamine).) 3c-B-3 0 ~ ~ CH3 232C 69.0 (The product is present as a hydrate (0.25 mol of H20 per mol of melamine).) OH
3c-B-4 0 ~ ~ OCH3 240C ~' 70 (The product is present as a hydrate (0.25 mol of OH
f120 per mol of melamine).) , \
3c-B-5 0 ~H3 262'C 75.2 (The product is present as a hydrate (0.1 mol of H20 CH per mol of melamine).) 3c-B-6 0 ~ ~ 268'C 89~ ~e Pr~uct is present as a hycfrate (0.15 mol of H20 per mol of melamine).) ~~~~~~'~
Table 3d:
Comp. n R Melting Yield [!o of No. point theory]
230C (ACter84.3 (The product purifi- is present 3d-B-1 0 OCH3 canon via as a hcmihydrate.
the hydro--~ chloride 210C.) 77,4 (Prepared by treating OCH3 3d-B-1 with HCl.
Recrystallisation from 3d-B-2 I ~ ~ 258C water in the presence of OCH3 activated carbon.
The product is present as a OCH3 hydrate (0.75 mol of H20 per mol of melamine).) 30.1 (Addition of dimethyl-3d-B-3 0 ~ ~ Cl 200C acetamide. Purifjcation by rcprecipitation using dimethyl sulfoxidc/I-I20).
CI .
22.1 (Addition of dimethyl-3d-B-4 0 Cl 150C acetamide. Purification by reprecipitation using dimethyl sulfoxide/H20).
Cl Cl i CI
91,7 (The productis / \ present 3d-B-5 0 OH > 300C as a hydrate (0.4 mol of H2U per mol of Cl melamine).) I
I
Example 9: A dry mixture comprising 100 parts of S-PVC (~Vinnol H 70 DF), 17 parts of dioctyl phthalate, 3 parts of epoxidised Soya bean oil, 0.33 part of zinc oleate, 0.53 part of barium p-(t-butyl)benzoate, 0.7 part of diisodecylphenyl phosphite, 0.44 part of ~SHELL
SOL A (aromatic hydrocarbon mixture) and 0.2 part of the melamine derivative listed in Tables 4a to 4h is rolled on mixing rolls at 190°C for 5 minutes. Test specimens of the 0.3 mm thick rolled sheet formed are subjected to thermal stress at 180°C in a test oven (~Mathi:; Thermotester). After the interval given, the: "yellowness index"
(YI) according to ASTM D 1925 is determined on a test specimen. The results are listed in Tables 4a to 4h.
Table 4a:
Mclamina YI
derivative after exposure time in minutes without 9.2 17.6 16.8 15.7 13.8 Compow~d 4.1 5.1 5.2 5.3 6.3 2a-A-4 Compowid 2.0 8.1 7.7 7.8 8.3 3a-B-14 Table 4b:
Melamine YI
derivative after exposure time in minutes without 10.4 14.4 15.4 16.6 16.8 Compow~d 5.5 6.7 6.6 7.7 9.0 Table 4c:
Melamin~: YI
derivative after exposure time in minutes without 9.7 12.3 14.6 16.3 17.0 Compowtd 5.7 7.7 7.9 7.7 8.2 3a-B-18 Compowtd SS 6S 6.5 7.0 7.4 3a-B-19 Compowtd 3a-B-20 5.3 6.0 6.5 7.0 7.3 ~~~~~Y~z -2f>-Table 4d:
Melamine YI
derivative after exposure time in minutes without 9.8 12.0 13.5 15.8 17.1 Compound 5.7 6.4 7.4 7.5 7.8 ~
3a-B-1 Compound 5.4 6.5 6.7 7.0 7.3 3a-B-2 Compound 3a-B-3 5.3 7.0 7.5 7.4 7.6 Compound 3a-B-4 5.2 6.3 6.6 7.0 7.0 Compound 3a-B-5 5.6 7.3 7.3 7.6 8.3 Table 4e:
Melamine n derivative after exposure time in minutes IS
without 9.0 14.8 16.7 17.4 17.1 Compound 3,3 4.5 5.0 5.5 6.5 3b-B-1 Compound 3.2 4.8 4.7 5.1 5.6 3b-B-2 Compound 3b-B-3 2.9 4.4 5.0 5.2 5.8 Compound 3b-B-4 3.3 3.6 4.2 4.6 5.5 Compound 3b-B-5 2.7 3.5 3.7 4.7 4.9 Table 4f:
Melamine YI
derivative after exposure time in minutes without 8.4 13.8 15.0 16.3 16.5 Compound 3.0 4.4 4.6 4.9 5.9 Table 4g:
Melamine YI
derivative after exposure time in minutes without 8.3 13.7 15.1 17.6 17.9 Compound 3.1 4.3 4.6 5.0 5.8 3a-B-8 Compound 3.p 5.1 6.0 6.1 6.3 3 a-B-10 Compotmd 4.3 5.2 5.7 6.6 7 3a-B-II .
Compound 3.8 5.6 6.2 6.7 8 3b-B-l.i .
Compotmd 4.3 5.7 5.9 7.1 7.6 3b-B-15 Table 4h:
Melamine YI
derivative after exposure time in minutes without 10,7 16.4 18.3 17.9 17.9 Compound 3.5 4.8 5.2 5.9 6.4 3b-B-2') Compound 3.1 4.2 5.0 5.2 6.1 3b-B-6 ~~~~~'~~
Example 10: A dry mixture comprising 100 parts of P'VC ( ~2 Solvic 2~4 GA), 3 parts of epoxidised Soya bean oil, 0.35 part of calcium stearate, 0.15 part of zinc stearate, 0.55 part of diisodecylphenyl phosphite, and 0.3 part of the melamine derivative listed in Tables Sa to 5k is rolled on mixing rolls at 180°C for 5 minutes. Test specimens of the 0.3 mm thick rolled sheet formed are subjected to thermal stress at 180°C in a test oven (~Mathis Thermotester). After the interval given, the "yellowness index" (YI) according to ASTM
D 1925 is determined on a test specimen. The results are listed in Tables 5a to 5k.
Table Sa:
Yl after exposure time in minutes Melamine derivative IS
without 20.1 25.1 29.9 31.8 28.1 31.6 62.8 Compound 2a-A-3 2.6 4.7 4.0 6.9 10.5 18.7 35.7 Table Sb:
Melamine YI
derivative after exposure time in minutes S
without 19.5 27.6 30.5 33.4 30.2 I
Compound 3.4 4.9 5.9 7.6 12.8 Table 5c:
Melamine YI
derivative after exposure time in minutes I
S
without 22.4 37.4 38.5 36.9 41.2 Compound 2.7 7.1 10.3 14.7 24.5 3a-B-19 Compound 3.2 8.3 10.6 15.0 24.7 3a-B-20 ~
~~3~~'~2 Table Sd:
Melamine n derivative after exposure time in minutes without 1G.9 36.6 36.4 34.9 53.3 Compotutd 36-B-5 2.5 10.4 12.8 16.6 26.6 Table Se:
Melamine n derivative after exposure time in minutes without 17.5 36.2 36.8 345 33.3 Compound 3d-B-1 1.9 4.8 6.8 10.0 15.8 Table Sf:
Melamine n derivative after exposure time in minutes IS
without 18.0 38.3 38.5 34.7 37.0 Compottrtd 2c-A-1 3.6 6.1 8.8 13.3 18.2 Table SQ:
Melamine YI
derivative after exposure time in minutes IS
without 16.3 37.8 38.2 34.2 44.7 Compotutd 3a-B-12 2.8 7.0 9.4 14.0 23.7 Table Sh:
Melamine YI
derivative after exposure time in minutes without . 17.5 36.3 37.4 57.2 79.0 Compotutd 2a-All 3.2 9.2 11.8 16.6 21.8 Compound 3 a-B-15 3.1 I 1.1 13.1 17.6 24.
I
Table Si:
Melamim: YI
derivative after exposure time in minutes without 15.7 36.2 37.3 49.3 74.0 Compotutd 3a-B-13 6.2 11.4 12.6 15.6 20.6 Table Si:
Melamine YI
derivative after exposure time in minutes without 17.0 38.4 37.5 33.8 44.5 Compound 36-B-11 .2.1 6.6 8.5 10.6 12.8 t I t Table Sk:
Melamine YI
derivative after exposure time in minutes without 15.0 32.1 37.7 36.9 31.8 Compotmd 3b-B-20 1.5 5.0 5.7 7.4 11.9 Example 11: A dry mixture comprising 100 parts of S-PVC (~Vinnol H 70 DF), 17 parts of dioctyl phthalate, 3 parts of epoxidised soya bean oil, 0.33 part of zinc oleate, 0.53 part of barium p-(t-butyl)benzoate, 0.7 part of diisodecylphenyl phosphite, 0.44 part of butyldiglycol and 0.2 part of the melamine derivative listed in Table 6 is rolled on mixing rolls at 190°C for 5 minutes. Test specimens of the 0.3 mm thick rolled sheet formed are subjected to thermal stress at 180°C in a test oven (~Mathis Thermotester). After the interval given, the "yellowness index" (YI) according to ASTM D 1925 is determined on a test specimen. The results are listed in Table 6.
Table 6:
Melamine derivativeYI
after exposure time in minutes without 9.211.613.615.2 18.518.7 17.415.9 14.6 15.1 Compound 2a-A-3 2.83.0 3.2 3.7 3.8 4.3 5.2 5.1 5.5 7.7
Claims (13)
1. A composition comprising a) a chlorine-containing polymer, b) 0.01 to 0.9% by weight, relative to the chlorine-containing polymer, of a compound of the formula I and/or its hydrochloride, in which R is C7-C11phenylalkyl, C7-C11phenylalkyl which is substituted on the phenyl by 1 to 3 radicals, these radicals, independently of one another, being hydroxyl, chlorine, C1-C4alkyl, methoxy or ethoxy, or R is further more a group of the formula IIb, in which R1, R2 and R3, independently of one another, are hydrogen, C1-C20alkyl, C1-C20alkyloxy, C1-C20alkylthio, C2-C12alkyloxycarbonyl, C2-C12alkanoyl, phenyl, phenyloxy, phenylthio, hydroxyl, mercapto or chlorine, and c) 0.01 to 5% by weight, relative to the chlorine-containing polymer, of an Me(II) carboxylate and/or Me(II)-phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
2. A composition according to claim 1 with the proviso that component c) is a mixture of barium/zinc carboxylates if component b) is phenylmelamine.
3. A composition according to claim 1, in which R is benzyl, benzyl which is substituted on the phenyl by 1 to 3 radicals, these radicals, independently of one another, being hydroxyl, chlorine, C1-C4alkyl, methoxy or ethoxy, or R is furthermore a group of the formula IIb, in which R1, R2 and R3, independently of one another, are hydrogen, C1-C10alkyl, C1-C10alkyloxy, C8-C18alkylthio, C2-C12alkyloxycarbonyl, C2-C6alkanoyl, phenyloxy, phenylthio, hydroxyl, mercapto or chlorine.
4. A composition according to claim 1, in which R is benzyl.
5. A composition according to claim 1, in which R is a group of the formula IIb.
6. A composition according to claim 1, in which R is a group of the formula IIb and the radicals R1, R2 and R3, independently of one another, are hydrogen, C1-C4alkyl, C1-C4alkyloxy, C8-C16alkylthio, C2-C12alkyloxycarbonyl, hydroxyl, mercapto or chlorine.
7. A composition according to claim 1, in which R is a group of the formula IIb, R1 is hydrogen, R2 and R3, independently of one another, are C1-C4alkyl, C1-C4alkyloxy, C8-C16alkylthio, C2-Cl2alkyloxycarbonyl, hydroxyl or chlorine, and R2 is additionally hydrogen.
8. A composition according to claim 1, in which R is a group of the formula IIb, R1 and R2 are hydrogen and R3 is C1-C4alkyl, C1-C4alkyloxy, C8-C16alkylthio, C2-C12alkyloxycarbonyl, hydroxyl or chlorine.
9. A composition according to claim 1, in which component b) is the hydrochloride of a compound of the formula I.
10. A composition according to any one of claims 1 or 2 to 9, in which component c) is an Me(II) carboxylate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
11. A composition according to any one of claims 1 or 2 to 9, in which component c) is a mixture of barium/zinc carboxylates and/or calcium/zinc carboxylates.
12. A composition according to any one of claims 1 to 11, in which component a) is polyvinyl chloride.
13. A process for stabilising a chlorine-containing polymer against thermodegradation, which comprises incorporating in the chlorine-containing polymer components b) and c) according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH56/90-1 | 1990-01-09 | ||
| CH5690 | 1990-01-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2033672A1 CA2033672A1 (en) | 1991-07-10 |
| CA2033672C true CA2033672C (en) | 2001-03-13 |
Family
ID=4178306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2033672 Expired - Lifetime CA2033672C (en) | 1990-01-09 | 1991-01-07 | Melamine derivatives as stabilisers for chlorine-containing polymers |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0437186B1 (en) |
| JP (1) | JP3018203B2 (en) |
| CA (1) | CA2033672C (en) |
| DE (1) | DE59009953D1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08239534A (en) * | 1995-03-01 | 1996-09-17 | Nissan Chem Ind Ltd | Resin composition, containing halogen and stabilized against heat and light |
| WO1999036411A1 (en) * | 1998-01-19 | 1999-07-22 | Nissan Chemical Industries, Ltd. | Method for modifying melamine derivatives |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3084135A (en) * | 1960-06-08 | 1963-04-02 | Heyden Newport Chemical Corp | Vinyl halide compositions stabilized with melamine |
| GB1102857A (en) * | 1965-10-19 | 1968-02-14 | American Cyanamid Co | Combination of uv absorbers and melamine derivatives as stabilizers for rigid poly (vinyl chloride) |
| JPS546043A (en) * | 1977-06-17 | 1979-01-17 | Nippon Carbide Ind Co Ltd | Deodorizer for formed products of vinyl chloride resin and method of film forming utilizing the same |
-
1990
- 1990-12-27 DE DE59009953T patent/DE59009953D1/en not_active Expired - Lifetime
- 1990-12-27 EP EP90811033A patent/EP0437186B1/en not_active Expired - Lifetime
-
1991
- 1991-01-07 CA CA 2033672 patent/CA2033672C/en not_active Expired - Lifetime
- 1991-01-09 JP JP3012721A patent/JP3018203B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04331250A (en) | 1992-11-19 |
| EP0437186B1 (en) | 1995-12-06 |
| EP0437186A1 (en) | 1991-07-17 |
| DE59009953D1 (en) | 1996-01-18 |
| JP3018203B2 (en) | 2000-03-13 |
| CA2033672A1 (en) | 1991-07-10 |
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