CA1336600C - Thiouracils as stabilizers for chlorine-containing polymers - Google Patents
Thiouracils as stabilizers for chlorine-containing polymersInfo
- Publication number
- CA1336600C CA1336600C CA 606793 CA606793A CA1336600C CA 1336600 C CA1336600 C CA 1336600C CA 606793 CA606793 CA 606793 CA 606793 A CA606793 A CA 606793A CA 1336600 C CA1336600 C CA 1336600C
- Authority
- CA
- Canada
- Prior art keywords
- c4alkyl
- substituted
- phenyl
- chlorine
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/56—One oxygen atom and one sulfur atom
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Composition containing a) a chlorine-containing polymer and b) at leastone compound of the formula I
(I) in which n is 1 or 2, R1 is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12-phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2 is C1-C18alkyl, a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl, or R2 is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-Cl2phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb ' (IIa) (IIb) in which X1 is C1-C17alkyl, C3-C17alkenyl, C5-C7cycloalkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, C1-C10alkylthio or di(C1-C4alkyl)amino, and X2 is C1-C18alkyl, C3-C18alkenyl, C5-C7cyclo-alkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y is hydrogen, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y is a group IIc or IId, (IIc) (IId) in which X3 is C1-C12alkylene or phenylene and X4 is C2-C12alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the provisos that the radicals Y and R2 are identical, if R2 is di(C1-C4-alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and the compound 3,6-dimethyl-2-thiouracil is excluded.
Composition containing a) a chlorine-containing polymer, b) the compound 3,6-dimethyl-2-thiouracil and c) an epoxy compound.
Novel compounds of the formula I are also described.
(I) in which n is 1 or 2, R1 is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12-phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2 is C1-C18alkyl, a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl, or R2 is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-Cl2phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb ' (IIa) (IIb) in which X1 is C1-C17alkyl, C3-C17alkenyl, C5-C7cycloalkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, C1-C10alkylthio or di(C1-C4alkyl)amino, and X2 is C1-C18alkyl, C3-C18alkenyl, C5-C7cyclo-alkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y is hydrogen, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y is a group IIc or IId, (IIc) (IId) in which X3 is C1-C12alkylene or phenylene and X4 is C2-C12alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the provisos that the radicals Y and R2 are identical, if R2 is di(C1-C4-alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and the compound 3,6-dimethyl-2-thiouracil is excluded.
Composition containing a) a chlorine-containing polymer, b) the compound 3,6-dimethyl-2-thiouracil and c) an epoxy compound.
Novel compounds of the formula I are also described.
Description
133660~
A-17150/+/CGM 321 Thiouracils as stabilizers for chlorine-containing polymers The present invention relates to chlorine-containing polymers stabilized with 2-thiouracils against thermal degradation and to novel 2-thio-uracils.
It is known that chlorine-containing polymers have to be protected against the damaging effect of light and heat, in particular when they are processed to moulded articles. 2-Thiouracils and their use as stabilizers have been disclosed, for example, in US-A 4,105,627, JP-A 81/11,936, JP-A 77/049,260 and JP-A 76/088,542.
The use of a number of uracils and thiouracils as herbicides is known in particular from FR-A 1,270,771 and CH-A 482,402.
A possible preparation process for thiouracils is described in ChemicalAbstracts 70:87730e (1969).
The present invention relates to compositions containing a) a chlorine-containing polymer and b) at least one compound of the formula I
R2~N ~S
0= / 3 Z ~ Y (I) \R -n in which n is 1 or 2, Rl is C1-C1galkyl, C3-C18alkenyl, phenyl, C7-C12-phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2 is C1-C18alkyl, a group -CH2~HCH2XR3 H
A-17150/+/CGM 321 Thiouracils as stabilizers for chlorine-containing polymers The present invention relates to chlorine-containing polymers stabilized with 2-thiouracils against thermal degradation and to novel 2-thio-uracils.
It is known that chlorine-containing polymers have to be protected against the damaging effect of light and heat, in particular when they are processed to moulded articles. 2-Thiouracils and their use as stabilizers have been disclosed, for example, in US-A 4,105,627, JP-A 81/11,936, JP-A 77/049,260 and JP-A 76/088,542.
The use of a number of uracils and thiouracils as herbicides is known in particular from FR-A 1,270,771 and CH-A 482,402.
A possible preparation process for thiouracils is described in ChemicalAbstracts 70:87730e (1969).
The present invention relates to compositions containing a) a chlorine-containing polymer and b) at least one compound of the formula I
R2~N ~S
0= / 3 Z ~ Y (I) \R -n in which n is 1 or 2, Rl is C1-C1galkyl, C3-C18alkenyl, phenyl, C7-C12-phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2 is C1-C18alkyl, a group -CH2~HCH2XR3 H
- 2 - 2148g-7778 or C2-C2zalkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl, or R2 is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, di~C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb -~Xl , -~OX2 (IIa) (IIb) in which X1 is C1-C17alkyl, C3-C17alkenyl, C5-C7cycloalkyl, C1-C4alkyl-substituted Cs-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, C1-C1~alkyithio or di(C1-C4alkyl)amino, and X2 is C1-C18alkyl, C3-C18alkenyl, C5-C7cyclo-alkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-C1zphenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is l, Y is hydrogen, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y is a group IIc or IId, -~-X3-&- ' -o-X4-o-(IIc) (IId) in which X3 is C1-C12alkylene or phenylene and X4 is C2-C12alkylene or C4-Cgalkylene which is interrupted by 1 or 2 oxygen atoms, with the provisos that the radicals Y and R2 are identical, if R2 is di(C1-C4-alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and the compound 3,6-dimethyl-2-thiouracil is excluded, &r:d further containing, if required, at least one Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, ed or Zn.
Alkyl of up to 18 carbon atoms is, for example, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, isooctyl, isononyl, n-decyl, n-dodecyl or n-octadecyl. R1 is preferably C1-C4alkyl, in particular methyl. One of the preferred meanings of Rz is C1-C12alkyl, for example C1-C4alkyl or C4-C1zalkyl.
Alkenyl of up to 18 carbon atoms is, for example, allyl, 2-methallyl, hexenyl, decenyl, undecenyl, heptadecenyl or oleyl. Preferred meanings for R2 as alkenyl are, for example, allyl and oleyl. In the alkenyl radicals, the carbon atom in the 1-position is preferably a saturated C atom.
Examples of C7-C1zphenylalkyl, whic.h can be unsubstituted or substituted on the phenyl ring by C1-C4alkyl and/or chlorine, are benzyl, 2-phenyl-ethyl, methylbenzyl, dimethylbenzyl, t-butylbenzyl and chlorobenzyl.
Benzyl is preferred.
The group -CH2C,HCH2XR3 is preferably 3-(2-ethylhexyl)oxy-2-hydroxypropyl OH
or 3-(2-ethylhexyl)thio-2-hydroxypropyl.
Cz-C22alkyl, in particular C2-C1zalkyl, which is substituted by hydroxyl or a group -XR3 is, for example, 2-hydroxyethyl, 2-methoxyethyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 9,10-dihydroxystearyl or 2,3,4,5,6-pentahydroxyhexyl. Hydroxyl- or C1-C6alkyloxy-substituted C2-C6alkyl is preferred. 2-Hydroxyethyl and 2-methoxyethyl are particularly preferred.
The OH group and the group -XR3 are preferably not in the 1-position.
Examples of di(C1-C4alkyl)thiocarbamoyl are the following groups:
CH3 ~ C2Hs ~ C3H7 ~ C4Hg ~ ~CH3 ~ CZHs ~ C3H7 ~ C4Hg Examples of Cs-C7cycloalkyl which is unsubstituted or substituted by C1-C4alkyl are cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl or t-butylcyclohexyl. Cyclohexyl is preferred.
Phenyl which is substituted by C1-C4alkyl and/or chlorine is, for example, chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl, methylphenyl, dimethylphenyl, 2-methyl-6-ethylphenyl, 2-methyl-6-tert-butylphenyl, 4-tert-butylphenyl or 3-chloro-2-methylphenyl.
~ ~ 4 ~ 133 6SO O
Examples of C1~C1oalkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio and decylthio. Octylthio is preferred.
Di(C1-C4alkyl)amino is, for example, dimethylamino, diethylamino, dipropylamino and dibutylamino. Dimethylamino and diethylamino are preferred.
Examples of alkylene of up to 12 carbon atoms are methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, hepta-methylene, octamethylene, nonamethylene, decamethylene and dodeca-methylene.
C4-Cgalkylene which is interrupted by 1 or 2 oxygen atoms is, for example, 3-oxapentamethylene or 3,6-dioxaoctamethylene.
Preference is given to compositions in which n is 1, Rz is C1-C1~alkyl, a roup -CHzÇHCHzXR3, Cz-Czzalkyl which is substituted by hydroxyl or a OH
group -XR3, C3-C1galkenyl, C7-C1zphenylalkyl or C7-C1zphenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and Y is hydrogen.
Compositions in which n is 1 and Y is di(C1-C4alkyl)thiocarbamoyl or a group IIa or IIb are also of interest.
Particular preference is given to compositions in which n is 1, R1 is C1-C4alkyl or phenyl, R2 is C1-C1galkyl, hydroxyl- or C1-C6alkyloxy-sub-stituted Cz-C6alkyl, C3-C18alkenyl, benzyl or benzoyl, Y is hydrogen, di(C1-C4alkyl)thiocarbamoyl or a group IIa or IIb, X1 is C1-Clzalkyl, phenyl, dichlorophenyl, C1-Cloalkylthio or di(C1-C4alkyl)amino and Xz is C1-C1zalkyl.
Compositions in which n is 1, R1 is methyl, Rz is C1-C4alkyl, 2-hydroxy-ethyl, 2-methoxyethyl or allyl and Y is hydrogen, benzoyl or (C1-C1z~
alkyl)oxycarbonyl are also of particular interest.
Rl is preferably Cl-C4alkyl or phenyl.
R2 is preferably Cl-Cl8alkyl, hydroxyl- or Cl-C6alkyloxy-substituted C2-C6alkyl, C3-Clgalkenyl, benzyl or benzoyl.
The invention further relates to compositions containing a) a chlorine-containing polymer, b) at least one compound of the formula IA
R2\N ~S
O / ~ ~ y (IA) \R -n in which n is 1 or 2, Rl is Cl-Cl8alkyl, C3-Cl8alkenyl, phenyl, C7-Cl2-phenylalkyl or C7-Clzphenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, R2 is Cl-Clgalkyl, a group -CH21CHCHzXR3 or C2-Cz2alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is Cl-Cl8alkyl, phenyl or C7-Clzphenylalkyl, or R2 is furthermore C3-Cl8alkenyl, C7-Cl2phenylalkyl, C7-Clzphenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, di(Cl-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, -C~X~ OX2 (IIa) (IIb) in which Xl is Cl-Cl7alkyl, C3-Cl7alkenyl, Cs-C7cycloalkyl, Cl-C4alkyl-substituted Cs-C7cycloalkyl, phenyl, Cl-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-Clzphenylalkyl, C7-Clzphenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, Cl-Cloalkylthio or di(Cl-C4alkyl)amino and X2 is Cl-Cl8alkyl, C3-Clgalkenyl, Cs-C7cyclo-alkyl, Cl-C4alkyl-substituted C5-C7cycloalkyl, phenyl, Cl-C4alkyl- and/or chlorine-substituted phenyl, C7-Cl2phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, and, if n is 1, Y is hydrogen, di(Cl-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y is a group IIc or IId, -~-X3-~ O-X4-0(~- ' (IIc) (IId) in which X3 iS Cl-Cl zalkylene or phenylene and X4 is C2-Cl2alkylene or C4-C8alkylene which is interrupted by l or 2 oxygen atoms, with the proviso that the radicals Y and R2 are identical, if R2 is di(Cl-C4-alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and c) an ep~xy compound, and further cont~in;n~ if required, at least one Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is ~a, Ca, Mg, Cd or Zn.
The compound of the formula IA is preferably 3,6-dimethyl-2-thiouracil.
The epoxy compound preferably consists of epoxidized oils and epoxidized fatty acid esters, for example epoxidized soybean oil and epoxidized butyl oleate.
The chlorine-containing polymers are preferably vinyl chloride homopoly-mers or vinyl chloride copolymers. Examples of suitable comonomers for the copolymers are: vinyl acetate, vinylidene chloride, trans-dichloro-ethylene, ethylene, propylene, butylene, maleic acid, acrylic acid, fumaric acid, itaconic acid. Further suitable chlorine-containing polymers are post-chlorinated PVC and chlorinated polyolefins, further-more graft polymers of PVC with EVA, ABS and MBS. Preferred substrates also include mixtures of the abovementioned homopolymers and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic or/and elastomeric polymers, in particular with ABS, MBS, NBR, SAN, EVA.
Preference is also given to suspension and bulk polymers and to emulsion polymers.
Polyvinyl chloride is particularly preferred as chlorine-containing polymer.
It is advantageous to use the compounds of the formula I or IA togetherwith known heat stabilizers, for example organotin compounds, lead compounds, organic antimony compounds, Me(II) phenolates, in particular C7-C20alkylphenolates, for example nonylphenolate, or Me(II) carboxy-~ - 7 - 1 3 3 6 6 0 0 lates. Me(II) is, for example, Ba, Ca, Mg, Cd or Zn. The carboxylates are preferably salts of carboxylic acids having 7 to 20 C atoms, for example benzoates, alkenoates or alkanoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or 2-ethylhexanoates. Particular preference is given to stearates, oleates and p-tert-butylbenzoates.
Examples of organotin compounds, lead compounds and organic antimony compounds are the compounds mentioned in US-A 4,743,640, column 3, line 48 to column 5, line 38.
Additionally, the chlorine-containing polymers stabilized with compounds of the formula I or IA can contain customary amounts of conventional PVC
stabilizers, for example phosphites, preferably those of the formulae AzO\P, A1O-P/ \-/ \P-OA2, [ /P-OCHzCH ~ 0, ~ P,-OCH2lCHOICHcH20 ~ -A30 O-- -0 A30 2 Al H3 H3 n in which Al, Az and A3, independently of one another, are C4-Clgalkyl, C6-Cl,3alkenyl, Cs-C7cycloalkyl, phenyl or phenyl substituted by one to three Cl-Clzalkyl groups.
Examples are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl,trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite. Preference is given to the aryldialkyl and the alkyldiaryl phosphites, for example phenyldidecyl, (2,4-di-tert-butylphenyl)didode-cyl, (2,6-di-tert-butylphenyl)didodecyl phosphite and the dialkyl penta-erythritol and diaryl pentaerythritol diphosphites, for example distearyl pentaerythritol diphosphite. Preference is also given to the tetraphenyl and tetraalkyl 1,2-dipropylene glycol diphosphites and the poly-1,2-di-propylene glycol phenyl phosphites and the poly-1,2-dipropylene glycol alkyl phosphites. Particularly preferred organic phosphites are distearyl pentaerythritol diphosphite, tris(nonylphenyl) phosphite, phenyl didecyl phosphite, tetraphenyl 1,2-dipropylene glycol diphosphite and poly-1,2-dipropylene glycol phenyl phosphite.
The invention therefore preferably relates to compositions containing, apart from component a) and a compound of the formula I, at least a Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn, and, if desired, a phosphite.
According to a further preference, the compositions according to the invention contain, apart from component a) and a compound of the formula I, at least one Me(II) carboxylate, in which Me(II) is Ba, Ca, Mg or Zn. Mixtures of Ba/Zn or Ca/Zn carboxylates are particularly preferred as costabilizers.
Preference is also given to compositions containing, apart from compo-nent a), a compound of the formula IA and component c), at least one Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn, and, if desired, a phosphite, in particular one of the abovementioned formulae.
The known heat stabilizers (for example carboxylates) can be present inthe material to be stabilized in a concentration known to one skilled in the art, for example in amounts of 0.05 to 5 % by weight.
The phosphites are used, for example, in concentrations of 0.3 to 5, preferably 0.5 to 1, % by weight, and the epoxy compounds, for example the epoxidized soybean oil, in concentrations of 1 to 8, preferably 1 to 3, % by weight.
The compounds of the formula I or IA are incorporated, for example, in amounts of 0.05 to 5, preferably 0.05 to 1, in particular 0.1 to 0.5, %
by weight in the chlorine-containing polymer.
The % by weight given refers in each case to the material to be stabilized.
Depending on the intended use of the polymers, it is also possible to in-corporate, before or during the incorporation of the stabilizers, further additives, for example phenolic antioxidants, lubricants (preferably montan waxes or glycerol esters), fatty acid esters, paraffins, plasti-cizers, fillers, carbon black, asbestos, kaolin, talc, glass fibres, modifiers (such as impact additives), optical brighteners, pigments, light stabilizers, UV absorbers, flame retardants or antistatics.
1~36600 21489-7778 Further possible additives ~re furthermore B-aminocrotonates, for example the compounds described in DE-A 804,442, DE-A 807,207 and JP-A 75/17,454, pyrrols, for example the compounds mentioned in EP-A 22,087, amino-uracils, for example the compounds disclosed in EP-A 65,934, aminothio-uracils, for example the compounds known from EP-A 41,479, polyols, for example the compounds described in DE-A 3,019,910, ~-diketones, for example the compounds mentioned in DE-A 2,600,516, or even mixtures of ~-diketones and hydrotalcites, as described, for example, in EP-A 63,180.
The incorporation of the stabilizer components in the chlorine-containing polymer is advantageously carried out as usual on mixing rolls, for example a 2-roll mill at temperatures between 150 and 200C. In general, sufficient homogenization can be achieved within 5 to 15 minutes. The components can be added individually or together as a premixture. A
liquid premixture has proven to be advantageous, that is to say, in-different solvents and/or plasticizers are present.
The invention also relates to the novel compounds of the formulae IIIA,IIIB, IIIC, IIID and IIIE, C~ ~S
oc.\ ~ -H (IIIA) \Rl ~
in which R1' is C3-Clgalkyl, C3-C1~alkenyl, C7-C1zphenylalkyl or C7-Cl2-phenylalkyl which is substituted on the phenyl ring by chlorine;
R~ ~S
0=-\ ~ -H (IIIB) ._.
.~ \.
!
~,./
in which R2' is Cl-C18alkyl, C3-C1galkenyl, C7-Clzphenylalkyl or C7-C1z-phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine;
~ o 13366 0 0 21489-7778 R 2 ~N ~S
0=-\ ~ -H (IIIC) .=.
in which R2" is C1o-C1galkyl or Clo-C1galkenyl;
R2" ' ~S
= ? :~ - H (IIID) \R l "
in which R1" is C1-C1galkyl, C3-C1galkenyl, phenyl, C7-C12phenylalkyl or C7-C1zphenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and Rz"' is a group -CH2~CHCH2XR3 or C2-C22alkyl H
which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is Cl-Clgalkyl, phenyl or C7-Clzphenylalkyl;
IV
Rz ~ ~S
0=-\ ~ Y' (IIIE) \R "' -n in which n is l or 2, Rl"' is Cl-C18alkyl, C3-C1galkenyl, phenyl, C7-C12phenylalkyl or C7-Clzphenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, Rz is Cl-Clgalkyl, a group -CH2lCHCH2XR3 or Cz-C22alkyl which is substituted by hydroxyl or a group H
-XR3, in which X is oxygen or sulfur and R3 is Cl-Clgalkyl, phenyl or c7-cl2phenylalkyl~ or R2 is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-Cl2phenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, di(Cl-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb X~ OX2 (IIa) (IIb) in which Xl is Cl-C17alkyl, C3-Cl7alkenyl, Cs-C7cycloalkyl, Cl-C4alkyl-substituted Cs-C7cycloalkyl, phenyl, Cl-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-Cl2phenylalkyl, C7-Cl2phenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, Cl-Cloalkylthio or 11- 1~36600 di(Cl-C4alkyl)amino and Xz is Cl-Cl8alkyl, C3-Cl8alkenyl, Cs-C7cyclo-alkyl, Cl-C4alkyl-substituted Cs-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-Cl2phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y' is di(Cl-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y' is a group IIc or IId, -8-X3-8- , -80-X4-08-(IIc) (IId) in which X3 is Cl-Cl2alkylene or phenylene and X4 is Cz-Cl2alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the proviso that R2I and Y' are identical, if R2 is di(Cl-C4alkyl)thio-carbamoyl or a group of the formula IIa or IIb.
Examples of Rl', Rl", Rl"', Rz', Rz", Rz"', Rz and Y' are those defined in formula I.
Preference is given to compounds of the formulae IIIA, IIIB and IIIC inwhich Rl' is C3-C4alkyl, R2' is Cl-Cl8alkyl, allyl or benzyl and R2" is C1o-Clgalkyl or allyl.
Preference is also given to compounds of the formula IIID in which Rl" is Cl-C4alkyl or phenyl and Rz"' is hydroxyl- or C1-C6alkyloxy-substituted C2 -C6alkyl .
Compounds of the formula IIIE in which n is 1, Rl"' is Cl-C4alkyl, Rz is C1-C4alkyl, allyl, benzyl or benzoyl and Y' is di(C1-C4alkyl)thio-carbamoyl or a group IIa or IIb, Xl is C1-C12alkyl, phenyl, dichloro-phenyl, C1-Cloalkylthio or di(Cl-C4alkyl)amino and Xz is C1-C1zalkyl are also of interest.
The compounds of the formula I can be prepared analogously to known processes.
A possible preparation process for compounds of the formula I in which Y
is hydrogen is described by the following equation:
Rl-C-CH2-CR-O-Z + RzNH-~-NH2 -HOZ il ~
-H20 Rl \~/ ~S
(IV) (V) (I) Z is, for example, Cl-C4alkyl, in particular methyl or ethyl. The reaction advantageously takes place under reflux conditions in the presence of a strong base in an organic solvent, preferably a short-chain alcohol, in particular methanol or ethanol. The reaction can also be carried out, for example, in IV as reaction medium at 60-120C. The bases are, for example, alkali metal alcoholates or alkali metal hydroxides, preferably sodium methoxide, sodium ethoxide, sodium hydroxide or potassium hydroxide. The reactants can be used, for example, in a stoichiometric ratio; a molar ratio of IV/V/base = (1.0-2.5)/1/~1.0-3.0) is preferred. After the reaction is completed, the product is isolated and purified by conventional methods.
The starting materials of the formulae IV and V are commercially avail-able or can be prepared in analogy to known processes. The compound of the formula V can be obtained, for example, according to the following reaction:
--ZlCl ZlSCN + Z 2 COCl ' Z2CONCS
Z 2 CONCS + R 2 NH 2 ' Z 2 CONH-C-NHR 2 (Va) Z2CONH-C-NHRz + NaOH - H2N-C-NHR2 + Z2COzNa (V) Zl is, for example, potassium, sodium or ammonium and Z2 iS, for example, methoxy, ethoxy or phenyl. The reaction advantageously takes place in an organic solvent, preferably acetone or ethyl acetate. It is also possible `~ - 13 - 1 3 3 6 6 00 to use the compound of the formula Va without cleaving off the protective group ZzC0- directly for the preparation of the compounds of the formula I.
The compounds of the formula I which are acylated in the 1- or 1- and 3-position can also be prepared in analogy to known processes; for example, by reaction of the sodium salt of the corresponding thiouracil with an acyl chloride.
Some compounds of the formula I can be obtained during the preparation as an isomeric mixture, which can be separated by conventional processes known to one skilled in the art.
R Rz R1 ~ ~S R1 N~ SY
(I) (I*) Formula I is therefore understood to include also the compounds of the formula I*.
The examples below illustrate the invention further. Parts and per-centages are by weight, unless stated otherwise.
Example 1: Preparation of 3,6-dimethyl-2-thiouracil.
~ y CH3 H3C y ~S
H
116.1 g (1 mole) of methyl acetoacetate are added dropwise to a solution of 216 g (1.2 mole) of 30 % sodium methoxide in 200 ml of abs. methanol.
90.2 g (1 mole) of N-methylthiourea are then added in portions with stirring. The reaction mixture is heated to reflux for 3 hours, in the course of which the initially clear solution gradually becomes more viscous. After the reaction is completed, the methanol is evaporated in _ - 14 - 1336600 vacuo, and the residue is taken up in 500 ml of water. The mixture obtained is neutralized with concentrated hydrochloric acid, liberating C02. The pH is then brought to 4-5 with 40 ml of glacial acetic acid. The resulting precipitate is filtered off with suction, washed with a water/methanol mixture (2:1) and dried. The product has a melting point of 276C. The yield is 122.5 g ( 78.4 % of theory).
Examples 2-6: The compounds listed in Table 1 are prepared in analogy to the process described in Example 1.
o il Y
R~ S
Table 1:
Ex. Rl R2 Melting point 2 -C3H7-n -CH3 162C (after reprecipitation from methylene chloride/isopropyl ether) 3 -C4Hg-t -CH3 156C (after reprecipitation from methylene chloride/isopropyl ether) 4 -CH3 -C2Hs 206C (after digestion with methanol) -CH3 -CH2-CH=CH2 185C (after washing with H20) -- 215C (after washing with H20, 6 -CH3 -CH2--~ ~- followed by recrystallization from =- DMF/ethanol) Example 7: Preparation of 3-n-octyl-6-methyl-2-thiouracil.
/- CgHl~-n il Y
H3C ~ ~S
A) Preparation of N-benzoyl-N'-n-octylthiourea. 150.7 g (1.55 mole) of potassium thiocyanate are added with stirring to 0.8 1 of acetone.
203.9 g (1.45 mole) of benzoyl chloride are then added dropwise at room temperature. The mixture obtained is heated to reflux for 10 minutes.
133660~
187.5 g (1.45 mole) of n-octylamine in 0.2 1 of acetone are added at such a rate that reflux is maintained (exothermic reaction). After the reaction is completed, the acetone is distilled off at atmospheric pressure. The highly visco~us residue (535.0 g) consists of N-benzoyl-N'-n-octylthiourea (421.1 g), potassium chloride and some potassium thio-cyanate. The residue can be used further without work-up.
B) Preparation of 3-n-octyl-6-methyl-2-thiouracil. 535.0 g of the residue obtained according to A) are added to 0.5 1 of absolute methanol, and the mixture is heated to reflux for 5 minutes. 576.0 g of a 30 % sodium methoxide solution and 2.7 g of water are then added dropwise at the boil (exothermic reaction), and the mixture is boiled for another 10 minutes.
174.2 g (1.5 mole) of methyl acetoacetate in 0.5 1 of absolute methanol are then added dropwise (slightly exothermic reaction), and the reaction mixture is heated to reflux for 20 hours. After the reaction is com-pleted, the methanol and the water of the reaction are distilled off.
0.5 1 of 5 % NaOH are added to the residue, and the mixture is heated to 50C for 30 minutes with stirring. The mixture is then diluted at room temperature with 3.0 1 of water, and the precipitate obtained (109.0 g of n-octylthiourea) is filtered off with suction. The strongly alkaline filtrate is acidified with concentrated hydrochloric acid (evolution of COz). The resulting precipitate is filtered off with suction, washed until free from chloride and dried to constant weight. The 3-n-octyl-6-methyl-2-thiouracil obtained has a melting point of 142C.
Example 8: Preparation of 3-(2-hydroxyethyl)-6-methyl-2-thiouracil.
~- C2H4OH
il Y
H3C ~/ ~S
27.9 g (0.232 mole) of N-(2-hydroxyethyl)thiourea are dissolved in 100 ml of absolute methanol. 29.0 g (0.25 mole) of methyl acetoacetate and 50.4 g (0.28 mole) of a 30 % methanolic sodium methoxide solution are added with stirring. After heating to reflux for 6 hours, the methanol is distilled off, the residue is dissolved in 150 ml of water and acidified with concentrated hydrochloric acid. The precipitate obtained is filtered ~ - 16 - 13 3 6 6 0 0 off with suction, washed until neutral and dried to constant weight. The product has a melting point of 200C. The yield is 23.0 g ( 53 % of theory).
Example 9: Preparation of 3-(n-butyl)-6-methyl-2-thiouracil. 0.125 moleof a 30 % sodium methoxide solution is added dropwise to a solution of 0.1 mole of N-(n-butyl)thiourea and 0.11 mole of methyl acetoacetate in 100 ml of absolute methanol with stirring. After refluxing for 8 hours, another 0.11 mole of methyl acetoacetate and 0.125 mole of sodium methoxide solution are added. The reaction mixture is then refluxed for another 16 hours. The methanol is then distilled off, and the residue is taken up in 200 ml of water. The solution is acidified with concentrated hydrochloric acid, the precipitate obtained is filtered off with suction, washed until neutral and dried to a constant weight. The product has a melting point of 164C. The yield is 80.8 % of theory.
Examples 10-16: The compounds listed in Table 2 are prepared and workedup in analogy to the process described in Example 9, unless stated otherwise.
.
H3C ~ ~S
Table 2:
Ex. Rz Reactants Reaction Yield time in ThioureaMethyl acetoacetate NaOMe hours Melting point -C8Hl7-i )i-Hl7CgNHCSNH2 1.2 ) 1.22) 10 0.52 154C (after recrystallization from a petroleum ether/iso-propyl ether mixture) 11 -CloH2l~n n-H2lCloNHCSNH2 0.22 ) 0.25 ) 24 93 %
0.1 12 ) -Cl2Hzs-n n-HzsCl2NHCSNH20.22 ) 0.25 ) 24 83.5 % _~
0.1 `~
13 ) -CgHl9-i )i-HlgCgNHCSNH20.22 ) 0.25 ) 24 74.6 %
0.1 14 ) Oleyl Oleyl-NHCSNH2 0.0704 ) o.o83) 24 93 % C~
0.032 C~3 97C (after recry- C5 stallization C5 from methanol) Ex..... Rz Reactants Reaction Yield Thiourea Methyl acetoacetate NaOMe hours Melting point (mol) (mol) (mol) 15 ) -ClgH37-n n-H37C1l3NHCSNH2 1.4 ) 1.4 ) 16 0.6 -C4Hg-i i-HgC4NHCSNH2 )0.66 ) 0.75 ) 24 _ - 19 - 1336600 Indices:
1 ) -CBHl 7-i corresponds to -CHz-ÇH-(CHz)3-CH3.
zHs 2) The compound is added in two portions. The first half is added at the beginning of the reaction, and the second half after a reaction time of 4 hours.
3) The compound is added in two portions. The first half is added at the beginning of the reaction, and the second half after a reaction time of 8 hours.
4) The residue is taken up in 250 ml of water and 100 ml of a 15 %
aqueous sodium hydroxide solution. The precipitate obtained is filtered off (recovery of 13 YO of the unconverted thiourea). The filtrate is acidified and worked up according to Example 9.
ÇH3 5) -C9H19-i corresponds to -CHz-CHz-,ÇH-CHz-~ CH3.
Alkyl of up to 18 carbon atoms is, for example, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, isooctyl, isononyl, n-decyl, n-dodecyl or n-octadecyl. R1 is preferably C1-C4alkyl, in particular methyl. One of the preferred meanings of Rz is C1-C12alkyl, for example C1-C4alkyl or C4-C1zalkyl.
Alkenyl of up to 18 carbon atoms is, for example, allyl, 2-methallyl, hexenyl, decenyl, undecenyl, heptadecenyl or oleyl. Preferred meanings for R2 as alkenyl are, for example, allyl and oleyl. In the alkenyl radicals, the carbon atom in the 1-position is preferably a saturated C atom.
Examples of C7-C1zphenylalkyl, whic.h can be unsubstituted or substituted on the phenyl ring by C1-C4alkyl and/or chlorine, are benzyl, 2-phenyl-ethyl, methylbenzyl, dimethylbenzyl, t-butylbenzyl and chlorobenzyl.
Benzyl is preferred.
The group -CH2C,HCH2XR3 is preferably 3-(2-ethylhexyl)oxy-2-hydroxypropyl OH
or 3-(2-ethylhexyl)thio-2-hydroxypropyl.
Cz-C22alkyl, in particular C2-C1zalkyl, which is substituted by hydroxyl or a group -XR3 is, for example, 2-hydroxyethyl, 2-methoxyethyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 9,10-dihydroxystearyl or 2,3,4,5,6-pentahydroxyhexyl. Hydroxyl- or C1-C6alkyloxy-substituted C2-C6alkyl is preferred. 2-Hydroxyethyl and 2-methoxyethyl are particularly preferred.
The OH group and the group -XR3 are preferably not in the 1-position.
Examples of di(C1-C4alkyl)thiocarbamoyl are the following groups:
CH3 ~ C2Hs ~ C3H7 ~ C4Hg ~ ~CH3 ~ CZHs ~ C3H7 ~ C4Hg Examples of Cs-C7cycloalkyl which is unsubstituted or substituted by C1-C4alkyl are cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl or t-butylcyclohexyl. Cyclohexyl is preferred.
Phenyl which is substituted by C1-C4alkyl and/or chlorine is, for example, chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl, methylphenyl, dimethylphenyl, 2-methyl-6-ethylphenyl, 2-methyl-6-tert-butylphenyl, 4-tert-butylphenyl or 3-chloro-2-methylphenyl.
~ ~ 4 ~ 133 6SO O
Examples of C1~C1oalkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio and decylthio. Octylthio is preferred.
Di(C1-C4alkyl)amino is, for example, dimethylamino, diethylamino, dipropylamino and dibutylamino. Dimethylamino and diethylamino are preferred.
Examples of alkylene of up to 12 carbon atoms are methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, hepta-methylene, octamethylene, nonamethylene, decamethylene and dodeca-methylene.
C4-Cgalkylene which is interrupted by 1 or 2 oxygen atoms is, for example, 3-oxapentamethylene or 3,6-dioxaoctamethylene.
Preference is given to compositions in which n is 1, Rz is C1-C1~alkyl, a roup -CHzÇHCHzXR3, Cz-Czzalkyl which is substituted by hydroxyl or a OH
group -XR3, C3-C1galkenyl, C7-C1zphenylalkyl or C7-C1zphenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and Y is hydrogen.
Compositions in which n is 1 and Y is di(C1-C4alkyl)thiocarbamoyl or a group IIa or IIb are also of interest.
Particular preference is given to compositions in which n is 1, R1 is C1-C4alkyl or phenyl, R2 is C1-C1galkyl, hydroxyl- or C1-C6alkyloxy-sub-stituted Cz-C6alkyl, C3-C18alkenyl, benzyl or benzoyl, Y is hydrogen, di(C1-C4alkyl)thiocarbamoyl or a group IIa or IIb, X1 is C1-Clzalkyl, phenyl, dichlorophenyl, C1-Cloalkylthio or di(C1-C4alkyl)amino and Xz is C1-C1zalkyl.
Compositions in which n is 1, R1 is methyl, Rz is C1-C4alkyl, 2-hydroxy-ethyl, 2-methoxyethyl or allyl and Y is hydrogen, benzoyl or (C1-C1z~
alkyl)oxycarbonyl are also of particular interest.
Rl is preferably Cl-C4alkyl or phenyl.
R2 is preferably Cl-Cl8alkyl, hydroxyl- or Cl-C6alkyloxy-substituted C2-C6alkyl, C3-Clgalkenyl, benzyl or benzoyl.
The invention further relates to compositions containing a) a chlorine-containing polymer, b) at least one compound of the formula IA
R2\N ~S
O / ~ ~ y (IA) \R -n in which n is 1 or 2, Rl is Cl-Cl8alkyl, C3-Cl8alkenyl, phenyl, C7-Cl2-phenylalkyl or C7-Clzphenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, R2 is Cl-Clgalkyl, a group -CH21CHCHzXR3 or C2-Cz2alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is Cl-Cl8alkyl, phenyl or C7-Clzphenylalkyl, or R2 is furthermore C3-Cl8alkenyl, C7-Cl2phenylalkyl, C7-Clzphenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, di(Cl-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, -C~X~ OX2 (IIa) (IIb) in which Xl is Cl-Cl7alkyl, C3-Cl7alkenyl, Cs-C7cycloalkyl, Cl-C4alkyl-substituted Cs-C7cycloalkyl, phenyl, Cl-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-Clzphenylalkyl, C7-Clzphenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, Cl-Cloalkylthio or di(Cl-C4alkyl)amino and X2 is Cl-Cl8alkyl, C3-Clgalkenyl, Cs-C7cyclo-alkyl, Cl-C4alkyl-substituted C5-C7cycloalkyl, phenyl, Cl-C4alkyl- and/or chlorine-substituted phenyl, C7-Cl2phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, and, if n is 1, Y is hydrogen, di(Cl-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y is a group IIc or IId, -~-X3-~ O-X4-0(~- ' (IIc) (IId) in which X3 iS Cl-Cl zalkylene or phenylene and X4 is C2-Cl2alkylene or C4-C8alkylene which is interrupted by l or 2 oxygen atoms, with the proviso that the radicals Y and R2 are identical, if R2 is di(Cl-C4-alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and c) an ep~xy compound, and further cont~in;n~ if required, at least one Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is ~a, Ca, Mg, Cd or Zn.
The compound of the formula IA is preferably 3,6-dimethyl-2-thiouracil.
The epoxy compound preferably consists of epoxidized oils and epoxidized fatty acid esters, for example epoxidized soybean oil and epoxidized butyl oleate.
The chlorine-containing polymers are preferably vinyl chloride homopoly-mers or vinyl chloride copolymers. Examples of suitable comonomers for the copolymers are: vinyl acetate, vinylidene chloride, trans-dichloro-ethylene, ethylene, propylene, butylene, maleic acid, acrylic acid, fumaric acid, itaconic acid. Further suitable chlorine-containing polymers are post-chlorinated PVC and chlorinated polyolefins, further-more graft polymers of PVC with EVA, ABS and MBS. Preferred substrates also include mixtures of the abovementioned homopolymers and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic or/and elastomeric polymers, in particular with ABS, MBS, NBR, SAN, EVA.
Preference is also given to suspension and bulk polymers and to emulsion polymers.
Polyvinyl chloride is particularly preferred as chlorine-containing polymer.
It is advantageous to use the compounds of the formula I or IA togetherwith known heat stabilizers, for example organotin compounds, lead compounds, organic antimony compounds, Me(II) phenolates, in particular C7-C20alkylphenolates, for example nonylphenolate, or Me(II) carboxy-~ - 7 - 1 3 3 6 6 0 0 lates. Me(II) is, for example, Ba, Ca, Mg, Cd or Zn. The carboxylates are preferably salts of carboxylic acids having 7 to 20 C atoms, for example benzoates, alkenoates or alkanoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or 2-ethylhexanoates. Particular preference is given to stearates, oleates and p-tert-butylbenzoates.
Examples of organotin compounds, lead compounds and organic antimony compounds are the compounds mentioned in US-A 4,743,640, column 3, line 48 to column 5, line 38.
Additionally, the chlorine-containing polymers stabilized with compounds of the formula I or IA can contain customary amounts of conventional PVC
stabilizers, for example phosphites, preferably those of the formulae AzO\P, A1O-P/ \-/ \P-OA2, [ /P-OCHzCH ~ 0, ~ P,-OCH2lCHOICHcH20 ~ -A30 O-- -0 A30 2 Al H3 H3 n in which Al, Az and A3, independently of one another, are C4-Clgalkyl, C6-Cl,3alkenyl, Cs-C7cycloalkyl, phenyl or phenyl substituted by one to three Cl-Clzalkyl groups.
Examples are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl,trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite. Preference is given to the aryldialkyl and the alkyldiaryl phosphites, for example phenyldidecyl, (2,4-di-tert-butylphenyl)didode-cyl, (2,6-di-tert-butylphenyl)didodecyl phosphite and the dialkyl penta-erythritol and diaryl pentaerythritol diphosphites, for example distearyl pentaerythritol diphosphite. Preference is also given to the tetraphenyl and tetraalkyl 1,2-dipropylene glycol diphosphites and the poly-1,2-di-propylene glycol phenyl phosphites and the poly-1,2-dipropylene glycol alkyl phosphites. Particularly preferred organic phosphites are distearyl pentaerythritol diphosphite, tris(nonylphenyl) phosphite, phenyl didecyl phosphite, tetraphenyl 1,2-dipropylene glycol diphosphite and poly-1,2-dipropylene glycol phenyl phosphite.
The invention therefore preferably relates to compositions containing, apart from component a) and a compound of the formula I, at least a Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn, and, if desired, a phosphite.
According to a further preference, the compositions according to the invention contain, apart from component a) and a compound of the formula I, at least one Me(II) carboxylate, in which Me(II) is Ba, Ca, Mg or Zn. Mixtures of Ba/Zn or Ca/Zn carboxylates are particularly preferred as costabilizers.
Preference is also given to compositions containing, apart from compo-nent a), a compound of the formula IA and component c), at least one Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn, and, if desired, a phosphite, in particular one of the abovementioned formulae.
The known heat stabilizers (for example carboxylates) can be present inthe material to be stabilized in a concentration known to one skilled in the art, for example in amounts of 0.05 to 5 % by weight.
The phosphites are used, for example, in concentrations of 0.3 to 5, preferably 0.5 to 1, % by weight, and the epoxy compounds, for example the epoxidized soybean oil, in concentrations of 1 to 8, preferably 1 to 3, % by weight.
The compounds of the formula I or IA are incorporated, for example, in amounts of 0.05 to 5, preferably 0.05 to 1, in particular 0.1 to 0.5, %
by weight in the chlorine-containing polymer.
The % by weight given refers in each case to the material to be stabilized.
Depending on the intended use of the polymers, it is also possible to in-corporate, before or during the incorporation of the stabilizers, further additives, for example phenolic antioxidants, lubricants (preferably montan waxes or glycerol esters), fatty acid esters, paraffins, plasti-cizers, fillers, carbon black, asbestos, kaolin, talc, glass fibres, modifiers (such as impact additives), optical brighteners, pigments, light stabilizers, UV absorbers, flame retardants or antistatics.
1~36600 21489-7778 Further possible additives ~re furthermore B-aminocrotonates, for example the compounds described in DE-A 804,442, DE-A 807,207 and JP-A 75/17,454, pyrrols, for example the compounds mentioned in EP-A 22,087, amino-uracils, for example the compounds disclosed in EP-A 65,934, aminothio-uracils, for example the compounds known from EP-A 41,479, polyols, for example the compounds described in DE-A 3,019,910, ~-diketones, for example the compounds mentioned in DE-A 2,600,516, or even mixtures of ~-diketones and hydrotalcites, as described, for example, in EP-A 63,180.
The incorporation of the stabilizer components in the chlorine-containing polymer is advantageously carried out as usual on mixing rolls, for example a 2-roll mill at temperatures between 150 and 200C. In general, sufficient homogenization can be achieved within 5 to 15 minutes. The components can be added individually or together as a premixture. A
liquid premixture has proven to be advantageous, that is to say, in-different solvents and/or plasticizers are present.
The invention also relates to the novel compounds of the formulae IIIA,IIIB, IIIC, IIID and IIIE, C~ ~S
oc.\ ~ -H (IIIA) \Rl ~
in which R1' is C3-Clgalkyl, C3-C1~alkenyl, C7-C1zphenylalkyl or C7-Cl2-phenylalkyl which is substituted on the phenyl ring by chlorine;
R~ ~S
0=-\ ~ -H (IIIB) ._.
.~ \.
!
~,./
in which R2' is Cl-C18alkyl, C3-C1galkenyl, C7-Clzphenylalkyl or C7-C1z-phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine;
~ o 13366 0 0 21489-7778 R 2 ~N ~S
0=-\ ~ -H (IIIC) .=.
in which R2" is C1o-C1galkyl or Clo-C1galkenyl;
R2" ' ~S
= ? :~ - H (IIID) \R l "
in which R1" is C1-C1galkyl, C3-C1galkenyl, phenyl, C7-C12phenylalkyl or C7-C1zphenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and Rz"' is a group -CH2~CHCH2XR3 or C2-C22alkyl H
which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is Cl-Clgalkyl, phenyl or C7-Clzphenylalkyl;
IV
Rz ~ ~S
0=-\ ~ Y' (IIIE) \R "' -n in which n is l or 2, Rl"' is Cl-C18alkyl, C3-C1galkenyl, phenyl, C7-C12phenylalkyl or C7-Clzphenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, Rz is Cl-Clgalkyl, a group -CH2lCHCH2XR3 or Cz-C22alkyl which is substituted by hydroxyl or a group H
-XR3, in which X is oxygen or sulfur and R3 is Cl-Clgalkyl, phenyl or c7-cl2phenylalkyl~ or R2 is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-Cl2phenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, di(Cl-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb X~ OX2 (IIa) (IIb) in which Xl is Cl-C17alkyl, C3-Cl7alkenyl, Cs-C7cycloalkyl, Cl-C4alkyl-substituted Cs-C7cycloalkyl, phenyl, Cl-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-Cl2phenylalkyl, C7-Cl2phenylalkyl which is substituted on the phenyl ring by Cl-C4alkyl and/or chlorine, Cl-Cloalkylthio or 11- 1~36600 di(Cl-C4alkyl)amino and Xz is Cl-Cl8alkyl, C3-Cl8alkenyl, Cs-C7cyclo-alkyl, Cl-C4alkyl-substituted Cs-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-Cl2phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y' is di(Cl-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y' is a group IIc or IId, -8-X3-8- , -80-X4-08-(IIc) (IId) in which X3 is Cl-Cl2alkylene or phenylene and X4 is Cz-Cl2alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the proviso that R2I and Y' are identical, if R2 is di(Cl-C4alkyl)thio-carbamoyl or a group of the formula IIa or IIb.
Examples of Rl', Rl", Rl"', Rz', Rz", Rz"', Rz and Y' are those defined in formula I.
Preference is given to compounds of the formulae IIIA, IIIB and IIIC inwhich Rl' is C3-C4alkyl, R2' is Cl-Cl8alkyl, allyl or benzyl and R2" is C1o-Clgalkyl or allyl.
Preference is also given to compounds of the formula IIID in which Rl" is Cl-C4alkyl or phenyl and Rz"' is hydroxyl- or C1-C6alkyloxy-substituted C2 -C6alkyl .
Compounds of the formula IIIE in which n is 1, Rl"' is Cl-C4alkyl, Rz is C1-C4alkyl, allyl, benzyl or benzoyl and Y' is di(C1-C4alkyl)thio-carbamoyl or a group IIa or IIb, Xl is C1-C12alkyl, phenyl, dichloro-phenyl, C1-Cloalkylthio or di(Cl-C4alkyl)amino and Xz is C1-C1zalkyl are also of interest.
The compounds of the formula I can be prepared analogously to known processes.
A possible preparation process for compounds of the formula I in which Y
is hydrogen is described by the following equation:
Rl-C-CH2-CR-O-Z + RzNH-~-NH2 -HOZ il ~
-H20 Rl \~/ ~S
(IV) (V) (I) Z is, for example, Cl-C4alkyl, in particular methyl or ethyl. The reaction advantageously takes place under reflux conditions in the presence of a strong base in an organic solvent, preferably a short-chain alcohol, in particular methanol or ethanol. The reaction can also be carried out, for example, in IV as reaction medium at 60-120C. The bases are, for example, alkali metal alcoholates or alkali metal hydroxides, preferably sodium methoxide, sodium ethoxide, sodium hydroxide or potassium hydroxide. The reactants can be used, for example, in a stoichiometric ratio; a molar ratio of IV/V/base = (1.0-2.5)/1/~1.0-3.0) is preferred. After the reaction is completed, the product is isolated and purified by conventional methods.
The starting materials of the formulae IV and V are commercially avail-able or can be prepared in analogy to known processes. The compound of the formula V can be obtained, for example, according to the following reaction:
--ZlCl ZlSCN + Z 2 COCl ' Z2CONCS
Z 2 CONCS + R 2 NH 2 ' Z 2 CONH-C-NHR 2 (Va) Z2CONH-C-NHRz + NaOH - H2N-C-NHR2 + Z2COzNa (V) Zl is, for example, potassium, sodium or ammonium and Z2 iS, for example, methoxy, ethoxy or phenyl. The reaction advantageously takes place in an organic solvent, preferably acetone or ethyl acetate. It is also possible `~ - 13 - 1 3 3 6 6 00 to use the compound of the formula Va without cleaving off the protective group ZzC0- directly for the preparation of the compounds of the formula I.
The compounds of the formula I which are acylated in the 1- or 1- and 3-position can also be prepared in analogy to known processes; for example, by reaction of the sodium salt of the corresponding thiouracil with an acyl chloride.
Some compounds of the formula I can be obtained during the preparation as an isomeric mixture, which can be separated by conventional processes known to one skilled in the art.
R Rz R1 ~ ~S R1 N~ SY
(I) (I*) Formula I is therefore understood to include also the compounds of the formula I*.
The examples below illustrate the invention further. Parts and per-centages are by weight, unless stated otherwise.
Example 1: Preparation of 3,6-dimethyl-2-thiouracil.
~ y CH3 H3C y ~S
H
116.1 g (1 mole) of methyl acetoacetate are added dropwise to a solution of 216 g (1.2 mole) of 30 % sodium methoxide in 200 ml of abs. methanol.
90.2 g (1 mole) of N-methylthiourea are then added in portions with stirring. The reaction mixture is heated to reflux for 3 hours, in the course of which the initially clear solution gradually becomes more viscous. After the reaction is completed, the methanol is evaporated in _ - 14 - 1336600 vacuo, and the residue is taken up in 500 ml of water. The mixture obtained is neutralized with concentrated hydrochloric acid, liberating C02. The pH is then brought to 4-5 with 40 ml of glacial acetic acid. The resulting precipitate is filtered off with suction, washed with a water/methanol mixture (2:1) and dried. The product has a melting point of 276C. The yield is 122.5 g ( 78.4 % of theory).
Examples 2-6: The compounds listed in Table 1 are prepared in analogy to the process described in Example 1.
o il Y
R~ S
Table 1:
Ex. Rl R2 Melting point 2 -C3H7-n -CH3 162C (after reprecipitation from methylene chloride/isopropyl ether) 3 -C4Hg-t -CH3 156C (after reprecipitation from methylene chloride/isopropyl ether) 4 -CH3 -C2Hs 206C (after digestion with methanol) -CH3 -CH2-CH=CH2 185C (after washing with H20) -- 215C (after washing with H20, 6 -CH3 -CH2--~ ~- followed by recrystallization from =- DMF/ethanol) Example 7: Preparation of 3-n-octyl-6-methyl-2-thiouracil.
/- CgHl~-n il Y
H3C ~ ~S
A) Preparation of N-benzoyl-N'-n-octylthiourea. 150.7 g (1.55 mole) of potassium thiocyanate are added with stirring to 0.8 1 of acetone.
203.9 g (1.45 mole) of benzoyl chloride are then added dropwise at room temperature. The mixture obtained is heated to reflux for 10 minutes.
133660~
187.5 g (1.45 mole) of n-octylamine in 0.2 1 of acetone are added at such a rate that reflux is maintained (exothermic reaction). After the reaction is completed, the acetone is distilled off at atmospheric pressure. The highly visco~us residue (535.0 g) consists of N-benzoyl-N'-n-octylthiourea (421.1 g), potassium chloride and some potassium thio-cyanate. The residue can be used further without work-up.
B) Preparation of 3-n-octyl-6-methyl-2-thiouracil. 535.0 g of the residue obtained according to A) are added to 0.5 1 of absolute methanol, and the mixture is heated to reflux for 5 minutes. 576.0 g of a 30 % sodium methoxide solution and 2.7 g of water are then added dropwise at the boil (exothermic reaction), and the mixture is boiled for another 10 minutes.
174.2 g (1.5 mole) of methyl acetoacetate in 0.5 1 of absolute methanol are then added dropwise (slightly exothermic reaction), and the reaction mixture is heated to reflux for 20 hours. After the reaction is com-pleted, the methanol and the water of the reaction are distilled off.
0.5 1 of 5 % NaOH are added to the residue, and the mixture is heated to 50C for 30 minutes with stirring. The mixture is then diluted at room temperature with 3.0 1 of water, and the precipitate obtained (109.0 g of n-octylthiourea) is filtered off with suction. The strongly alkaline filtrate is acidified with concentrated hydrochloric acid (evolution of COz). The resulting precipitate is filtered off with suction, washed until free from chloride and dried to constant weight. The 3-n-octyl-6-methyl-2-thiouracil obtained has a melting point of 142C.
Example 8: Preparation of 3-(2-hydroxyethyl)-6-methyl-2-thiouracil.
~- C2H4OH
il Y
H3C ~/ ~S
27.9 g (0.232 mole) of N-(2-hydroxyethyl)thiourea are dissolved in 100 ml of absolute methanol. 29.0 g (0.25 mole) of methyl acetoacetate and 50.4 g (0.28 mole) of a 30 % methanolic sodium methoxide solution are added with stirring. After heating to reflux for 6 hours, the methanol is distilled off, the residue is dissolved in 150 ml of water and acidified with concentrated hydrochloric acid. The precipitate obtained is filtered ~ - 16 - 13 3 6 6 0 0 off with suction, washed until neutral and dried to constant weight. The product has a melting point of 200C. The yield is 23.0 g ( 53 % of theory).
Example 9: Preparation of 3-(n-butyl)-6-methyl-2-thiouracil. 0.125 moleof a 30 % sodium methoxide solution is added dropwise to a solution of 0.1 mole of N-(n-butyl)thiourea and 0.11 mole of methyl acetoacetate in 100 ml of absolute methanol with stirring. After refluxing for 8 hours, another 0.11 mole of methyl acetoacetate and 0.125 mole of sodium methoxide solution are added. The reaction mixture is then refluxed for another 16 hours. The methanol is then distilled off, and the residue is taken up in 200 ml of water. The solution is acidified with concentrated hydrochloric acid, the precipitate obtained is filtered off with suction, washed until neutral and dried to a constant weight. The product has a melting point of 164C. The yield is 80.8 % of theory.
Examples 10-16: The compounds listed in Table 2 are prepared and workedup in analogy to the process described in Example 9, unless stated otherwise.
.
H3C ~ ~S
Table 2:
Ex. Rz Reactants Reaction Yield time in ThioureaMethyl acetoacetate NaOMe hours Melting point -C8Hl7-i )i-Hl7CgNHCSNH2 1.2 ) 1.22) 10 0.52 154C (after recrystallization from a petroleum ether/iso-propyl ether mixture) 11 -CloH2l~n n-H2lCloNHCSNH2 0.22 ) 0.25 ) 24 93 %
0.1 12 ) -Cl2Hzs-n n-HzsCl2NHCSNH20.22 ) 0.25 ) 24 83.5 % _~
0.1 `~
13 ) -CgHl9-i )i-HlgCgNHCSNH20.22 ) 0.25 ) 24 74.6 %
0.1 14 ) Oleyl Oleyl-NHCSNH2 0.0704 ) o.o83) 24 93 % C~
0.032 C~3 97C (after recry- C5 stallization C5 from methanol) Ex..... Rz Reactants Reaction Yield Thiourea Methyl acetoacetate NaOMe hours Melting point (mol) (mol) (mol) 15 ) -ClgH37-n n-H37C1l3NHCSNH2 1.4 ) 1.4 ) 16 0.6 -C4Hg-i i-HgC4NHCSNH2 )0.66 ) 0.75 ) 24 _ - 19 - 1336600 Indices:
1 ) -CBHl 7-i corresponds to -CHz-ÇH-(CHz)3-CH3.
zHs 2) The compound is added in two portions. The first half is added at the beginning of the reaction, and the second half after a reaction time of 4 hours.
3) The compound is added in two portions. The first half is added at the beginning of the reaction, and the second half after a reaction time of 8 hours.
4) The residue is taken up in 250 ml of water and 100 ml of a 15 %
aqueous sodium hydroxide solution. The precipitate obtained is filtered off (recovery of 13 YO of the unconverted thiourea). The filtrate is acidified and worked up according to Example 9.
ÇH3 5) -C9H19-i corresponds to -CHz-CHz-,ÇH-CHz-~ CH3.
6) The purity of the thiourea used is about 80 %.
7) The residue is taken up in 250 ml of water and 100 ml of a 15 %
aqueous sodium hydroxide solution, as a result of which it is dissolved.
The solution is acidified and worked up according to Example 9.
aqueous sodium hydroxide solution, as a result of which it is dissolved.
The solution is acidified and worked up according to Example 9.
8) The residue is taken up in 300 ml of water and 300 ml of ethyl acetate and acidified with concentrated HCl. The organic phase is separated off, washed with water, dried and concentrated.
9) The residue is heated in 1700 ml of a 20 YO aqueous sodium hydroxide solution for 15 minutes and poured onto 2.5 kg of ice and 1500 ml of acetone. The precipitate obtained is filtered off and dissolved in -3600 ml of ethanol. 44.3 % of the thiourea used can be recovered by fractional precipitation. Acidification of the combined filtrates gives 2-thiouracil.
10) The residue is taken up in 300 ml of water and 50 ml of methylene chloride and worked up according to Example 9.
Example 17: Preparation of 3-methyl-6-phenyl-2-thiouracil.
/ ~ yCH 3 S
The preparation is in analogy to Example 9. 0.3 mole of N-methylthiourea, 0.66 mole of ethyl benzoylacetate and 0.75 mole of sodium methoxide in the form of a 30 % methanolic sodium methoxide solution are used. Ethyl benzoylacetate and sodium methoxide are added to the reaction mixture in 2 portions. The addition of the first half takes place at the beginning of the reaction, and the second half is added after a reaction time of 10 hours. The reaction time is 24 hours. After the reaction is completed, the residue is dissolved in 100 ml of isopropyl ether and 300 ml of water, and acidified with concentrated hydrochloric acid. The precipitate obtained is worked up according to Example 9. The product has a melting point of 236C.
Example 18: Preparation of 3-(2'-methoxyethyl)-6-methyl-2-thiouracil.
~- y CH2CH20CH3 i! .
H3C ~ ~S
47.0 g (0.35 mole) of N-(2-methoxyethyl)thiourea are dissolved in 150 ml of abs. methanol. 69.7 g (0.60 mole) of methyl acetoacetate and 126 g (0.70 mole) of a 30 % methanolic sodium methoxide solution are added with stirring. The reaction mixture is heated to reflux for 19 hours. Methanol is then distilled off, and the residue obtained is dissolved in 200 ml of water and acidified with concentrated hydrochloric acid. The precipitate _ - 21 -obtained is filtered off with suction, washed until neutral and dried to a constant weight. The product has a melting point of 200C. The yield is 21.3 g ( 30.4 % of theory).
Example 19: Preparation of 1-benzoyl-3,6-dimethyl-2-thiouracil.
/- ~ CH3 .
H3C ~ ~S
In a 1 l three-neck flask, 53.5 g (0.34 mole) of 3,6-dimethyl-2-thio-uracil and 61.7 g (0.34 mole) of a 30 % sodium methoxide solution in 400 ml of abs. methanol are heated to reflux for 60 minutes with stirring. About 400 ml of methanol are then distilled off from the clear solution, and toluene is gradually added with heating until the boiling point of toluene is reached in the azeotropic distillation. The result is a heterogeneous suspension of a methanol-free thiouracil sodium salt.
Most of the toluene is then drawn off and replaced by 300 ml of dimethyl-acetamide, which gives a homogeneous solution of a methanol-free thio-uracil sodium salt. At 20C, 62.2 g (0.44 mole) of benzoyl chloride are then added dropwise, and the reaction mixture is stirred for 60 minutes.
The sodium chloride which precipitates is filtered off, and the filtrate is freed of volatile components in vacuo. The residue is treated with 300 ml of isopropyl ether*). The precipitate is filtered off. After drying, 77.6 g of an isomer mixture consisting of 1-benzoyl-3,6-di-methyl-2-thiouracil and 2-benzoylthio-3,6-dimethyl-4-oxo-3,4-dihydro-pyrimidine are obtained. The mixture is recrystallized from abs. acetone.
This gives colourless crystals which melt at 163C. According to the 1H-NMR spectrum, the mixture consists of 90 % of 1-benzoyl-3,6-dimethyl-2-thiouracil.
The isomeric mixture is treated with an aqueous bicarbonate solution, as a result of which the dihydropyrimidine is decomposed by hydrolysis.
1-Benzoyl-3,6-dimethyl-2-thiouracil, which has a melting point of 173C, can be separated off almost quantitatively in this manner.
*) The work-up can also be carried out, using bicarbonate solution instead of isopropyl ether. In this case, the desired thiouracil is obtained directly, and the dihydropyrimidine is lost.
Example 20: Preparation of 1,3-dibenzoyl-6-methyl-2-thiouracil.
n n coc6H5 il Y
H3C ~ ~S
OC6Hs In analogy to Example 19, a thiouracil disodium salt, which is present heterogeneously in toluene, is prepared from 85.3 g (0.6 mole) of 6-methyl-2-thiouracil, 216 g (1.2 mole) of a 30 ~o sodium methoxide solution in 500 ml of abs. methanol and toluene. The suspension is reacted under reflux for 3 hours with 168.7 g (1.2 mole) of benzoyl chloride. The sodium chloride obtained and unconverted thiouracil disodium salt are filtered off. The filtrate is freed from volatile components in vacuo, and the residue (115.3 g) is recrystallized from 600 ml of isopropanol/methylene chloride (5:1). The 1,3-dibenzoyl-6-methyl-2-thiouracil obtained has a melting point of 76C. The yield is 92.1 g ( 62.3 % of theory).
Examples 21-24: The compounds listed in Table 3 are prepared in analogyto Example 20.
Rz ~S
Y
Table 3:
Example R2 Y Yield Melting point 21 -CH3 -ICl-CllH23-n 42 %
116C (after recrystallization from acetone) 22 -CH3 -~O-CzHs 64.4 %
98C (after recrystallization from isopropylether) 23 -CHz-CH=CH2 -IC~-C6Hs 33-4 %
95C (after recrystallization from methylene chloride/petroleum ether) 24 ) -CHzC6Hs -ICl-C6Hs 35.2 %
163C (after recrystallization from methylene chloride/isopropyl ether) ) Present as a mixture of 1-benzoyl-3-benzyl-6-methyl-2-thiouracil and 2-benzoylthio-3-benzyl-6-methyl-4-oxo-3,4-dihydropyrimidine.
Example 25: Preparation of 1-isononanoyl-3,6-dimethyl-2-thiouracil.
~ CH3 ./y H3C ~ ~S
& CH3 31.2 g (0.2 mole) of 3,6-dimethyl-2-thiouracil and 36.0 g (0.2 mole) of a 30 % methanolic sodium methoxide solution are heated to reflux in 200 ml of abs. methanol for 2 hours. The methanol contained in the resulting clear solution is replaced by toluene by means of the azeotrope method.
The sodium salt suspension is concentrated by distilling off toluene. The addition of 150 ml of abs. dimethylacetamide gives a clear solution.
After the addition of 35.3 g (0.2 mole) of isononanoyl chloride, the reaction mixture is stirred overnight at room temperature. The solution is stirred into 600 ml of ice water, the precipitate is washed until _ - 24 -salt-free and dried to a constant weight. The product obtained is a 1:1 mixture of l-isononanoyl-3,6-dimethyl-2-thiouracil and 2-isononanoyl-thio-3,6-dimethyl-4-oxo-3,4-dihydropyrimidine. The yield is 56.6 g ( 95.4 ~O of theory).
The mixture of isomers which can be separated by chromatography has a melting point of 129C.
Example 26: Preparation of 1-(2',4'-dichlorobenzoyl)-3,6-dimethyl-2-thiouracil.
~ CH3 H3C ~S
~ Cl The preparation takes place in analogy to Example 25. The acylation reagent used is 2,4-dichlorobenzoyl chloride. 28.9 g ( 43.9 % of theory) of a 1.5:1 mixture of 1-(2',4'-dichlorobenzoyl)-3,6-dimethyl-2-thiouracil and 2-(2',4'-dichlorobenzoylthio)-3,6-dimethyl-4-oxo-3,4-dihydropyrimi-dine are obtained. The melting point of the mixture of isomers is 160C.
Pure 1-(2',4'-dichlorobenzoyl)-3,6-dimethyl-2-thiouracil can be obtained from the mixture of isomers by decomposition of the dihydropyrimidine by means of a NaOH solution.
Example 27: Preparation of 1-(2'-ethylhexyloxycarbonyl)-3,6-dimethyl-2-thiouracil.
R
/- ~ CH3 .
H3C ~ ~S
gO-CH2-CIH-(CH2)3-cH3 2Hs The preparation takes place in analogy to Example 25. The acylating reagent used is isooctyl chloroformate. After the addition of dimethyl-acetamide and acylating reagent, followed by stirring at room tempera-`~~ - 25 - 1336600 ture, the volatile components are evaporated in vacuo. The residue is boiled in petroleum ether, and the precipitate of sodium chloride formed is filtered off. The filtrate is concentrated down to the residue. The 1-(2'-ethylhexyloxycarbonyl)-3,6-dimethyl-2-thiouracil obtained is present as a viscous light-brown oil and has a refractive index of nD of 1.5360.
Example 28: Preparation of l-(n-octylthio)carbonyl-3,6-dimethyl-2-thiouracil il Y
H3C ~ ~S
~SC8Hl 7-n The preparation takes place in analogy to Example 25. The acylating reagent used is n-octyl thiochloroformate. After the reaction is com-pleted, the dimethylacetamide solution is stirred into ice water, and the mixture is extracted several times with methylene chloride. The organic phase is extracted with water, dried and then concentrated down to the residue. The residue is treated with petroleum ether, and the solution is filtered. The volatile components are removed from the filtrate in vacuo.
This gives a 4:1 mixture of 1-(n-octylthio)carbonyl-3,6-dimethyl-2-thio-uracil and 2-(n-octylthio)carbonylthio-3,6-dimethyl-4-oxo-3,4-dihydro-pyrimidine. The mixture of isomers is present as a colourless wax and has a melting point of 100C.
Example 29: Preparation of l-diethylcarbamoyl-3,6-dimethyl-2-thiouracil.
n \~
H3C ~ ~S
~N(C2Hs) 2 The preparation takes place in analogy to Example 25. The acylating reagent used is diethylcarbamoyl chloride. After the addition of di-methylacetamide and acylating reagent, followed by stirring at room temperature, the reaction mixture is concentrated down to the residue.
This residue is boiled in ether, the mixture is filtered, and the filtrate is again concentrated. The residue thus obtained is boiled in petroleum ether, and the precipitate formed is filtered off. l-Diethyl-carbamoyl-3,6-dimethyl-2-thiouracil is obtained as a colourless solid which has a melting point of 90C.
Example 30: Preparation of 1-dimethylthiocarbamoyl-3,6-dimethyl-2-thiouracil.
/~ ~ CH3 H3C ~ ~S
~N(CH3)z The preparation takes place in analogy to Example 25. The acylating reagent used is dimethylthiocarbamoyl chloride. After the reaction is completed, the dimethylacetamide solution is stirred into ice water, the precipitate obtained is filtered off, and the filtrate is extracted with methylene chloride. The organic phase is dried and concentrated down to the residue, which is treated with ether. A solid separates which is combined with the original precipitate. The product thus obtained is again treated with ether. 1-Dimethylthiocarbamoyl-3,6-dimethyl-2-thiouracil is present as a colourless solid which has a melting point of Example 31: A dry mixture consisting of 100 parts of S-PVC (K value 64), 3 parts of epoxidized soybean oil, 0.35 part of Ca stearate, 0.15 part of Zn stearate, 0.55 part of diisodecyl phenyl phosphite and 0.3 part of the stabilizer listed in Tables 4a to 4d is rolled on mixed rolls at 180C
for 5 minutes. This gives a 0.3 mm thick rolled sheet, of which samples are subjected to thermal stress in a testing oven (~Mathis Thermotester type LTF-ST) at 180C. The "yellowness index" (YI) of a sample according to ASTM D 1925 is determined over the time interval mentioned below. The results are summarized in Tables 4a to 4d.
. - 27 - 1 3 3 6 6 0 0 Table 4a:
YI after stress time in minutes Stabilizer 0 5 10 15 20 Without 19.120.1 24.6 32.4 37.3 Compound from1.9 2.1 2.7 4.5 15.5 Example 5 Compound from2.0 2.4 2.8 3.9 14.4 Example 6 Example 9 2.12.6 3.2 5.5 14.6 Table 4b:
. . YI after stress time in minutes Stabll1zer 0 5 10 15 Without 22.235.5 39.2 39.4 Compound from 5.1 5.7 7.0 11.4 Example 25 Table 4c:
Stabilizer YI after stress time in minutes Without 17.940.7 42.1 40.5 Compound from 2.0 4.3 8.1 15.7 Example 8 Compound from 2.3 3.4 5.1 15 Example 13 Table 4d:
YI after stress time in minutes Stablllzer 0 5 10 15 Without 17.637.6 40.241.0 Compound from 1.8 3.7 4.5 10.4 Example 7 Compound from 2.0 3.3 4.4 8.6 Example 10 compound from 3.4 4.5 5.8 9.5 Example 11 Compound from 1 9 3.2 5.4 14.7 Example 12 Example 32: A dry mixture consisting of 100 parts of S-PVC (K value 70), 17 parts of dioctylphthalate, 3 parts of epoxidized soybean oil, 0.33 part of Zn oleate, 0.53 part of Ba p-(t-butyl)benzoate, 0.7 part of diisodecyl phenyl phosphite, 0.44 part of ~Shell Sol A (aromatic hydro-carbon mixture) and 0.2 part of the stabilizer listed in Tables 5a to 5e is rolled on mixing rolls at 190C for 5 minutes. This gives a 0.3 mm thick rolled sheet, of which samples are subjected to thermal stress in a testing oven (~Mathis Thermotester) at 180C. The "yellowness index" (YI) of a sample according to ASTM D 1925 is determined over the time interval given. The results are summarized in Tables 5a to 5e.
Table 5a:
. .YI after stress time in minutes stablllzer 0 5 10 15 20 25 30 35 40 45 Without10.5 11.6 13.3 19.8 22.2 26.4 27.7 26.6 24.0 20.0 Compound from 0.4 0.6 0.91.2 1.4 2.2 4.6 5.4 8.6 13.3 Example 5 Compound from 0.1 0.6 0.90.9 1.5 1.9 2.7 4.2 7.0 9.6 Example 6 Example 9 0.3 0.3 0.5 0.41.1 1.3 2.6 4.0 6.1 8.7 Table 5b:
, . YI after stress time in minutes Stablllzer 0 5 10 15 30 Without 9.2 11.5 13.2 17.1 22.4 Compound from 1.4 1.9 2.3 2.6 3.1 Example 1 Compound from 1 9 2.1 2.5 2.7 3.2 Example 22 Compound from 2.9 3.4 3.5 4.0 5.2 Example 25 Compound from 2.1 2.8 3.0 3.2 4.1 Example 27 Compound from 1.7 2.4 2.7 3.7 5.7 Example 28 Table 5c:
. . YI after stress time in minutes Stablllzer 0 5 10 15 30 Without 9.8 20.4 24.7 25.8 26.6 Compound from 1.6 2.2 2.8 2.9 5.2 Compound from 1 o 1.7 2.0 2.6 3.5 Example 23 Compound from 1.7 2.1 2.9 3.1 3.4 Example 24 ~ - 30 - 13 3 6 6 ~ O
Table 5d:
. . YI after stress time in minutes Stablllzer 0 5 10 15 30 Uithout 8.1 17.0 20.2 23.0 23.4 Compound from 1.3 2.8 2.7 3.0 4.0 Example 4 Compound from 1.0 2.4 2.7 3.6 5.0 Example 8 Compound from 1.9 2.2 2.6 3.4 4.2 Example 13 Compound from 1.9 3.0 3.2 4.4 6.3 Example 21 Table 5e:
Stabilizer YI after stress time in minutes Without 10.6 13.0 16.3 19.7 22.8 Compound from 1.4 1.6 2.2 2.5 3.0 Example 7 Compound from Example 10 1.4 2.1 2.5 3.1 4.5 Compound from 1.8 3.0 3.1 3.1 4.3 Example 11 Compound from 1.7 2.1 2.6 2.8 4.0 Example 12 Example 33: A dry mixture consisting of 100 parts of S-PvC (K value 70), 17 parts of dioctylphthalate, 3 parts of epoxidized soybean oil, 0.26 part of ~Shell Sol A (aromatic hydrocarbon mixture), 0.48 part of Zn oleate, 0.54 part of Ba p-(t-butyl)benzoate, 0.64 part of diisodecyl phenyl phosphite, 0.06 part of 2,6-di-t-butyl-4-methylphenyl, 0.02 part of oleic acid and 0.2 part of the stabilizer listed in Table 6 is rolled on mixing rolls at 190C for 5 minutes. This gives a 0.3 mm thick rolled sheet, of which samples are subjected to thermal stress in a drying oven at 180C. The "yellowness index" (YI) of the samples according to ASTM D 1925 is determined over regular time intervals. The results are summarized in Table 6.
Table 6:
.YI after stress time in minutes Stablllzer0 10 20 30 40 50 60 Compound from 2.8 3.9 4.3 5.5 6.2 9.0 12.8 Example 1 Example 34: A dry mixture consisting of 100 parts of S-PVC (K value 64), 3 parts of epoxidized soybean oil, 0.35 part of Ca stearate, 0.15 part of Zn stearate, 0.55 part of diisodecyl phenyl phosphite and 0.3 part of the stabilizer listed in Table 7 is rolled on mixing rolls at 180C for 5 minutes. This gives a 0.3 mm thick rolled sheet, of which samples are irradiated in a ~Vitalux apparatus from ARA.
The following test conditions are present:
Without water spraying Radiation source: 8 Osram Vitalux lamps of 300 Watt each Standard temperature: 46C
Black panel temperature: 65C
No filter adjustment Tabelle 7:
Stabilizer YI after stress time in minutes Without 14.8 30.6 35.9 36.8 Compound from 1.6 3.1 5.1 16.6 Example 1 Compound from 1.5 3.1 5.3 13.8 Example 8
Example 17: Preparation of 3-methyl-6-phenyl-2-thiouracil.
/ ~ yCH 3 S
The preparation is in analogy to Example 9. 0.3 mole of N-methylthiourea, 0.66 mole of ethyl benzoylacetate and 0.75 mole of sodium methoxide in the form of a 30 % methanolic sodium methoxide solution are used. Ethyl benzoylacetate and sodium methoxide are added to the reaction mixture in 2 portions. The addition of the first half takes place at the beginning of the reaction, and the second half is added after a reaction time of 10 hours. The reaction time is 24 hours. After the reaction is completed, the residue is dissolved in 100 ml of isopropyl ether and 300 ml of water, and acidified with concentrated hydrochloric acid. The precipitate obtained is worked up according to Example 9. The product has a melting point of 236C.
Example 18: Preparation of 3-(2'-methoxyethyl)-6-methyl-2-thiouracil.
~- y CH2CH20CH3 i! .
H3C ~ ~S
47.0 g (0.35 mole) of N-(2-methoxyethyl)thiourea are dissolved in 150 ml of abs. methanol. 69.7 g (0.60 mole) of methyl acetoacetate and 126 g (0.70 mole) of a 30 % methanolic sodium methoxide solution are added with stirring. The reaction mixture is heated to reflux for 19 hours. Methanol is then distilled off, and the residue obtained is dissolved in 200 ml of water and acidified with concentrated hydrochloric acid. The precipitate _ - 21 -obtained is filtered off with suction, washed until neutral and dried to a constant weight. The product has a melting point of 200C. The yield is 21.3 g ( 30.4 % of theory).
Example 19: Preparation of 1-benzoyl-3,6-dimethyl-2-thiouracil.
/- ~ CH3 .
H3C ~ ~S
In a 1 l three-neck flask, 53.5 g (0.34 mole) of 3,6-dimethyl-2-thio-uracil and 61.7 g (0.34 mole) of a 30 % sodium methoxide solution in 400 ml of abs. methanol are heated to reflux for 60 minutes with stirring. About 400 ml of methanol are then distilled off from the clear solution, and toluene is gradually added with heating until the boiling point of toluene is reached in the azeotropic distillation. The result is a heterogeneous suspension of a methanol-free thiouracil sodium salt.
Most of the toluene is then drawn off and replaced by 300 ml of dimethyl-acetamide, which gives a homogeneous solution of a methanol-free thio-uracil sodium salt. At 20C, 62.2 g (0.44 mole) of benzoyl chloride are then added dropwise, and the reaction mixture is stirred for 60 minutes.
The sodium chloride which precipitates is filtered off, and the filtrate is freed of volatile components in vacuo. The residue is treated with 300 ml of isopropyl ether*). The precipitate is filtered off. After drying, 77.6 g of an isomer mixture consisting of 1-benzoyl-3,6-di-methyl-2-thiouracil and 2-benzoylthio-3,6-dimethyl-4-oxo-3,4-dihydro-pyrimidine are obtained. The mixture is recrystallized from abs. acetone.
This gives colourless crystals which melt at 163C. According to the 1H-NMR spectrum, the mixture consists of 90 % of 1-benzoyl-3,6-dimethyl-2-thiouracil.
The isomeric mixture is treated with an aqueous bicarbonate solution, as a result of which the dihydropyrimidine is decomposed by hydrolysis.
1-Benzoyl-3,6-dimethyl-2-thiouracil, which has a melting point of 173C, can be separated off almost quantitatively in this manner.
*) The work-up can also be carried out, using bicarbonate solution instead of isopropyl ether. In this case, the desired thiouracil is obtained directly, and the dihydropyrimidine is lost.
Example 20: Preparation of 1,3-dibenzoyl-6-methyl-2-thiouracil.
n n coc6H5 il Y
H3C ~ ~S
OC6Hs In analogy to Example 19, a thiouracil disodium salt, which is present heterogeneously in toluene, is prepared from 85.3 g (0.6 mole) of 6-methyl-2-thiouracil, 216 g (1.2 mole) of a 30 ~o sodium methoxide solution in 500 ml of abs. methanol and toluene. The suspension is reacted under reflux for 3 hours with 168.7 g (1.2 mole) of benzoyl chloride. The sodium chloride obtained and unconverted thiouracil disodium salt are filtered off. The filtrate is freed from volatile components in vacuo, and the residue (115.3 g) is recrystallized from 600 ml of isopropanol/methylene chloride (5:1). The 1,3-dibenzoyl-6-methyl-2-thiouracil obtained has a melting point of 76C. The yield is 92.1 g ( 62.3 % of theory).
Examples 21-24: The compounds listed in Table 3 are prepared in analogyto Example 20.
Rz ~S
Y
Table 3:
Example R2 Y Yield Melting point 21 -CH3 -ICl-CllH23-n 42 %
116C (after recrystallization from acetone) 22 -CH3 -~O-CzHs 64.4 %
98C (after recrystallization from isopropylether) 23 -CHz-CH=CH2 -IC~-C6Hs 33-4 %
95C (after recrystallization from methylene chloride/petroleum ether) 24 ) -CHzC6Hs -ICl-C6Hs 35.2 %
163C (after recrystallization from methylene chloride/isopropyl ether) ) Present as a mixture of 1-benzoyl-3-benzyl-6-methyl-2-thiouracil and 2-benzoylthio-3-benzyl-6-methyl-4-oxo-3,4-dihydropyrimidine.
Example 25: Preparation of 1-isononanoyl-3,6-dimethyl-2-thiouracil.
~ CH3 ./y H3C ~ ~S
& CH3 31.2 g (0.2 mole) of 3,6-dimethyl-2-thiouracil and 36.0 g (0.2 mole) of a 30 % methanolic sodium methoxide solution are heated to reflux in 200 ml of abs. methanol for 2 hours. The methanol contained in the resulting clear solution is replaced by toluene by means of the azeotrope method.
The sodium salt suspension is concentrated by distilling off toluene. The addition of 150 ml of abs. dimethylacetamide gives a clear solution.
After the addition of 35.3 g (0.2 mole) of isononanoyl chloride, the reaction mixture is stirred overnight at room temperature. The solution is stirred into 600 ml of ice water, the precipitate is washed until _ - 24 -salt-free and dried to a constant weight. The product obtained is a 1:1 mixture of l-isononanoyl-3,6-dimethyl-2-thiouracil and 2-isononanoyl-thio-3,6-dimethyl-4-oxo-3,4-dihydropyrimidine. The yield is 56.6 g ( 95.4 ~O of theory).
The mixture of isomers which can be separated by chromatography has a melting point of 129C.
Example 26: Preparation of 1-(2',4'-dichlorobenzoyl)-3,6-dimethyl-2-thiouracil.
~ CH3 H3C ~S
~ Cl The preparation takes place in analogy to Example 25. The acylation reagent used is 2,4-dichlorobenzoyl chloride. 28.9 g ( 43.9 % of theory) of a 1.5:1 mixture of 1-(2',4'-dichlorobenzoyl)-3,6-dimethyl-2-thiouracil and 2-(2',4'-dichlorobenzoylthio)-3,6-dimethyl-4-oxo-3,4-dihydropyrimi-dine are obtained. The melting point of the mixture of isomers is 160C.
Pure 1-(2',4'-dichlorobenzoyl)-3,6-dimethyl-2-thiouracil can be obtained from the mixture of isomers by decomposition of the dihydropyrimidine by means of a NaOH solution.
Example 27: Preparation of 1-(2'-ethylhexyloxycarbonyl)-3,6-dimethyl-2-thiouracil.
R
/- ~ CH3 .
H3C ~ ~S
gO-CH2-CIH-(CH2)3-cH3 2Hs The preparation takes place in analogy to Example 25. The acylating reagent used is isooctyl chloroformate. After the addition of dimethyl-acetamide and acylating reagent, followed by stirring at room tempera-`~~ - 25 - 1336600 ture, the volatile components are evaporated in vacuo. The residue is boiled in petroleum ether, and the precipitate of sodium chloride formed is filtered off. The filtrate is concentrated down to the residue. The 1-(2'-ethylhexyloxycarbonyl)-3,6-dimethyl-2-thiouracil obtained is present as a viscous light-brown oil and has a refractive index of nD of 1.5360.
Example 28: Preparation of l-(n-octylthio)carbonyl-3,6-dimethyl-2-thiouracil il Y
H3C ~ ~S
~SC8Hl 7-n The preparation takes place in analogy to Example 25. The acylating reagent used is n-octyl thiochloroformate. After the reaction is com-pleted, the dimethylacetamide solution is stirred into ice water, and the mixture is extracted several times with methylene chloride. The organic phase is extracted with water, dried and then concentrated down to the residue. The residue is treated with petroleum ether, and the solution is filtered. The volatile components are removed from the filtrate in vacuo.
This gives a 4:1 mixture of 1-(n-octylthio)carbonyl-3,6-dimethyl-2-thio-uracil and 2-(n-octylthio)carbonylthio-3,6-dimethyl-4-oxo-3,4-dihydro-pyrimidine. The mixture of isomers is present as a colourless wax and has a melting point of 100C.
Example 29: Preparation of l-diethylcarbamoyl-3,6-dimethyl-2-thiouracil.
n \~
H3C ~ ~S
~N(C2Hs) 2 The preparation takes place in analogy to Example 25. The acylating reagent used is diethylcarbamoyl chloride. After the addition of di-methylacetamide and acylating reagent, followed by stirring at room temperature, the reaction mixture is concentrated down to the residue.
This residue is boiled in ether, the mixture is filtered, and the filtrate is again concentrated. The residue thus obtained is boiled in petroleum ether, and the precipitate formed is filtered off. l-Diethyl-carbamoyl-3,6-dimethyl-2-thiouracil is obtained as a colourless solid which has a melting point of 90C.
Example 30: Preparation of 1-dimethylthiocarbamoyl-3,6-dimethyl-2-thiouracil.
/~ ~ CH3 H3C ~ ~S
~N(CH3)z The preparation takes place in analogy to Example 25. The acylating reagent used is dimethylthiocarbamoyl chloride. After the reaction is completed, the dimethylacetamide solution is stirred into ice water, the precipitate obtained is filtered off, and the filtrate is extracted with methylene chloride. The organic phase is dried and concentrated down to the residue, which is treated with ether. A solid separates which is combined with the original precipitate. The product thus obtained is again treated with ether. 1-Dimethylthiocarbamoyl-3,6-dimethyl-2-thiouracil is present as a colourless solid which has a melting point of Example 31: A dry mixture consisting of 100 parts of S-PVC (K value 64), 3 parts of epoxidized soybean oil, 0.35 part of Ca stearate, 0.15 part of Zn stearate, 0.55 part of diisodecyl phenyl phosphite and 0.3 part of the stabilizer listed in Tables 4a to 4d is rolled on mixed rolls at 180C
for 5 minutes. This gives a 0.3 mm thick rolled sheet, of which samples are subjected to thermal stress in a testing oven (~Mathis Thermotester type LTF-ST) at 180C. The "yellowness index" (YI) of a sample according to ASTM D 1925 is determined over the time interval mentioned below. The results are summarized in Tables 4a to 4d.
. - 27 - 1 3 3 6 6 0 0 Table 4a:
YI after stress time in minutes Stabilizer 0 5 10 15 20 Without 19.120.1 24.6 32.4 37.3 Compound from1.9 2.1 2.7 4.5 15.5 Example 5 Compound from2.0 2.4 2.8 3.9 14.4 Example 6 Example 9 2.12.6 3.2 5.5 14.6 Table 4b:
. . YI after stress time in minutes Stabll1zer 0 5 10 15 Without 22.235.5 39.2 39.4 Compound from 5.1 5.7 7.0 11.4 Example 25 Table 4c:
Stabilizer YI after stress time in minutes Without 17.940.7 42.1 40.5 Compound from 2.0 4.3 8.1 15.7 Example 8 Compound from 2.3 3.4 5.1 15 Example 13 Table 4d:
YI after stress time in minutes Stablllzer 0 5 10 15 Without 17.637.6 40.241.0 Compound from 1.8 3.7 4.5 10.4 Example 7 Compound from 2.0 3.3 4.4 8.6 Example 10 compound from 3.4 4.5 5.8 9.5 Example 11 Compound from 1 9 3.2 5.4 14.7 Example 12 Example 32: A dry mixture consisting of 100 parts of S-PVC (K value 70), 17 parts of dioctylphthalate, 3 parts of epoxidized soybean oil, 0.33 part of Zn oleate, 0.53 part of Ba p-(t-butyl)benzoate, 0.7 part of diisodecyl phenyl phosphite, 0.44 part of ~Shell Sol A (aromatic hydro-carbon mixture) and 0.2 part of the stabilizer listed in Tables 5a to 5e is rolled on mixing rolls at 190C for 5 minutes. This gives a 0.3 mm thick rolled sheet, of which samples are subjected to thermal stress in a testing oven (~Mathis Thermotester) at 180C. The "yellowness index" (YI) of a sample according to ASTM D 1925 is determined over the time interval given. The results are summarized in Tables 5a to 5e.
Table 5a:
. .YI after stress time in minutes stablllzer 0 5 10 15 20 25 30 35 40 45 Without10.5 11.6 13.3 19.8 22.2 26.4 27.7 26.6 24.0 20.0 Compound from 0.4 0.6 0.91.2 1.4 2.2 4.6 5.4 8.6 13.3 Example 5 Compound from 0.1 0.6 0.90.9 1.5 1.9 2.7 4.2 7.0 9.6 Example 6 Example 9 0.3 0.3 0.5 0.41.1 1.3 2.6 4.0 6.1 8.7 Table 5b:
, . YI after stress time in minutes Stablllzer 0 5 10 15 30 Without 9.2 11.5 13.2 17.1 22.4 Compound from 1.4 1.9 2.3 2.6 3.1 Example 1 Compound from 1 9 2.1 2.5 2.7 3.2 Example 22 Compound from 2.9 3.4 3.5 4.0 5.2 Example 25 Compound from 2.1 2.8 3.0 3.2 4.1 Example 27 Compound from 1.7 2.4 2.7 3.7 5.7 Example 28 Table 5c:
. . YI after stress time in minutes Stablllzer 0 5 10 15 30 Without 9.8 20.4 24.7 25.8 26.6 Compound from 1.6 2.2 2.8 2.9 5.2 Compound from 1 o 1.7 2.0 2.6 3.5 Example 23 Compound from 1.7 2.1 2.9 3.1 3.4 Example 24 ~ - 30 - 13 3 6 6 ~ O
Table 5d:
. . YI after stress time in minutes Stablllzer 0 5 10 15 30 Uithout 8.1 17.0 20.2 23.0 23.4 Compound from 1.3 2.8 2.7 3.0 4.0 Example 4 Compound from 1.0 2.4 2.7 3.6 5.0 Example 8 Compound from 1.9 2.2 2.6 3.4 4.2 Example 13 Compound from 1.9 3.0 3.2 4.4 6.3 Example 21 Table 5e:
Stabilizer YI after stress time in minutes Without 10.6 13.0 16.3 19.7 22.8 Compound from 1.4 1.6 2.2 2.5 3.0 Example 7 Compound from Example 10 1.4 2.1 2.5 3.1 4.5 Compound from 1.8 3.0 3.1 3.1 4.3 Example 11 Compound from 1.7 2.1 2.6 2.8 4.0 Example 12 Example 33: A dry mixture consisting of 100 parts of S-PvC (K value 70), 17 parts of dioctylphthalate, 3 parts of epoxidized soybean oil, 0.26 part of ~Shell Sol A (aromatic hydrocarbon mixture), 0.48 part of Zn oleate, 0.54 part of Ba p-(t-butyl)benzoate, 0.64 part of diisodecyl phenyl phosphite, 0.06 part of 2,6-di-t-butyl-4-methylphenyl, 0.02 part of oleic acid and 0.2 part of the stabilizer listed in Table 6 is rolled on mixing rolls at 190C for 5 minutes. This gives a 0.3 mm thick rolled sheet, of which samples are subjected to thermal stress in a drying oven at 180C. The "yellowness index" (YI) of the samples according to ASTM D 1925 is determined over regular time intervals. The results are summarized in Table 6.
Table 6:
.YI after stress time in minutes Stablllzer0 10 20 30 40 50 60 Compound from 2.8 3.9 4.3 5.5 6.2 9.0 12.8 Example 1 Example 34: A dry mixture consisting of 100 parts of S-PVC (K value 64), 3 parts of epoxidized soybean oil, 0.35 part of Ca stearate, 0.15 part of Zn stearate, 0.55 part of diisodecyl phenyl phosphite and 0.3 part of the stabilizer listed in Table 7 is rolled on mixing rolls at 180C for 5 minutes. This gives a 0.3 mm thick rolled sheet, of which samples are irradiated in a ~Vitalux apparatus from ARA.
The following test conditions are present:
Without water spraying Radiation source: 8 Osram Vitalux lamps of 300 Watt each Standard temperature: 46C
Black panel temperature: 65C
No filter adjustment Tabelle 7:
Stabilizer YI after stress time in minutes Without 14.8 30.6 35.9 36.8 Compound from 1.6 3.1 5.1 16.6 Example 1 Compound from 1.5 3.1 5.3 13.8 Example 8
Claims (17)
1. A composition containing a) a chlorine-containing polymer and b) at least one compound of the formula I
(I) in which n is 1 or 2, R1 is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12-phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2 is C1-C18alkyl, a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl, or R2 is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb ' (IIa) (IIb) in which X1 is C1-C17alkyl, C3-C17alkenyl, C5-C7cycloalkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, C1-C10alkylthio or di(C1-C4alkyl)amino, and X2 is C1-C18alkyl, C3-C18alkenyl, C5-C7cyclo-alkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y is hydrogen, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y is a group IIc or IId, , (IIc) (IId) in which X3 is C1-C12alkylene or phenylene and X4 is C2-C12alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the provisos that the radicals Y and R2 are identical, if R2 is di(C1-C4-alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and the compound 3,6-dimethyl-2-thiouracil is excluded; and further containing, if required, at least one Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
(I) in which n is 1 or 2, R1 is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12-phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2 is C1-C18alkyl, a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl, or R2 is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb ' (IIa) (IIb) in which X1 is C1-C17alkyl, C3-C17alkenyl, C5-C7cycloalkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, C1-C10alkylthio or di(C1-C4alkyl)amino, and X2 is C1-C18alkyl, C3-C18alkenyl, C5-C7cyclo-alkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y is hydrogen, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y is a group IIc or IId, , (IIc) (IId) in which X3 is C1-C12alkylene or phenylene and X4 is C2-C12alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the provisos that the radicals Y and R2 are identical, if R2 is di(C1-C4-alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and the compound 3,6-dimethyl-2-thiouracil is excluded; and further containing, if required, at least one 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, in which n is 1, R2 is C1-C18-alkyl, a group , C2-C22alkyl which is substituted by hydroxyl or a group -XR3, C3-C18alkenyl, C7-C12phenylalkyl or C7-C12-phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and Y is hydrogen.
3. A composition according to claim 1, in which n is 1 and Y is di(C1-C4-alkyl)thiocarbamoyl or a group IIa or IIb.
4. A composition according to claim 1, in which n is 1, R1 is C1-C4alkyl or phenyl, R2 is C1-C18alkyl, hydroxyl- or C1-C6alkyloxy-substituted C2-C6alkyl, C3-Cl8alkenyl, benzyl or benzoyl, Y is hydrogen, di(C1-C4-alkyl)thiocarbamoyl or a group IIa or IIb, X1 is C1-C12alkyl, phenyl, dichlorophenyl, C1-C10alkylthio or di(C1-C4alkyl)amino and X2 is C1-C12-alkyl.
5. A composition according to claim 1, in which n is 1, R1 is methyl, R2 is C1-C4alkyl, 2-hydroxyethyl, 2-methoxyethyl or allyl and Y is hydrogen, benzoyl or (C1-C12alkyl)oxycarbonyl.
6. A composition according to claim 1, in which R1 is C1-C4alkyl or phenyl.
7. A composition according to claim 1, in which R1 is methyl.
8. A composition according to claim 1, in which R2 is C1-C18alkyl, hydroxyl- or C1-C6alkyloxy-substituted C2-C6alkyl, C3-C18alkenyl, benzyl or benzoyl.
9. A composition according to claim 1, additionally containing at least one Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
10. A composition according to claim 1, additionally containing at least one Me(II) carboxylate, in which Me(II) is Ba, Ca, Mg or Zn.
11. A composition containing a) a chlorine-containing polymer, b) at least one compound of the formula IA
(IA) in which n is 1 or 2, R1 is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12-phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2 is C1-C18alkyl, a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl, or R2 is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, , (IIa) (IIb) in which X1 is C1-C17 alkyl, C3-C17 alkenyl, C5 -C7 cycloalkyl, Cl-C4 alkyl-substituted C5-C7cycloalkyl, phenyl, Cl-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, C1-C10alkylthio or di(C1-C4alkyl)amino and X2 is C1-C18alkyl, C3-C18alkenyl, C5-C7cyclo-alkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y is hydrogen, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y is a group IIc or IId, , (IIc) (IId) in which X3 is C1-C12alkylene or phenylene and X4 is C2-C12alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the proviso that the radicals Y and R2 are identical, if R2 is di(C1-C4-alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and c) an epoxy compound ; and further containing, if required, at least one Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
(IA) in which n is 1 or 2, R1 is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12-phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2 is C1-C18alkyl, a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl, or R2 is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, , (IIa) (IIb) in which X1 is C1-C17 alkyl, C3-C17 alkenyl, C5 -C7 cycloalkyl, Cl-C4 alkyl-substituted C5-C7cycloalkyl, phenyl, Cl-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, C1-C10alkylthio or di(C1-C4alkyl)amino and X2 is C1-C18alkyl, C3-C18alkenyl, C5-C7cyclo-alkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y is hydrogen, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y is a group IIc or IId, , (IIc) (IId) in which X3 is C1-C12alkylene or phenylene and X4 is C2-C12alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the proviso that the radicals Y and R2 are identical, if R2 is di(C1-C4-alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and c) an epoxy compound ; and further containing, if required, at least one Me(II) carboxylate and/or Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
12. A composition according to claim 11, additionally containing at least one Me(II) carboxylate andlor Me(II) phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
13. A composition according to claim 11, in which the compound of the formula IA is 3,6-dimethyl-2-thiouracil.
14. A compound of the formulae IIIA, IIIB, IIIC, IIID and IIIE
(IIIA) in which R1' is C3-C18alkyl, C3-C18alkenyl, C7-C12phenylalkyl or C7-C12-phenylalkyl which is substituted on the phenyl ring by chlorine;
(IIIB) in which R2' is C1-C18alkyl, C3-C18alkenyl, C7-C12phenylalkyl or C7-C12-phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine;
(IIIC) in which R2" is C10-C18alkyl or C10-C18alkenyl;
(IIID) in which Rl" is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and R2"' is a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl;
(IIIE) in which n is 1 or 2, Rl"' is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2IV is C1-C18alkyl, a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl, or R2IV is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb ' (IIa) (IIb) in which X1 is C1-C17alkyl, C3-C17alkenyl, C5-C7cycloalkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, C1-C10alkylthio or di(C1-C4alkyl)amino and X2 is C1-C18alkyl, C3-C18alkenyl, C5-C7cyclo-alkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y' is di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y' is a group IIc or IId, , (IIc) (IId) in which X3 is C1-C12alkylene or phenylene and X4 is C2-C12alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the proviso that R2IV and Y' are identical, if R2IV is di(C1-C4alkyl)thio-carbamoyl or a group of the formula IIa or IIb.
(IIIA) in which R1' is C3-C18alkyl, C3-C18alkenyl, C7-C12phenylalkyl or C7-C12-phenylalkyl which is substituted on the phenyl ring by chlorine;
(IIIB) in which R2' is C1-C18alkyl, C3-C18alkenyl, C7-C12phenylalkyl or C7-C12-phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine;
(IIIC) in which R2" is C10-C18alkyl or C10-C18alkenyl;
(IIID) in which Rl" is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and R2"' is a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl;
(IIIE) in which n is 1 or 2, Rl"' is C1-C18alkyl, C3-C18alkenyl, phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, R2IV is C1-C18alkyl, a group or C2-C22alkyl which is substituted by hydroxyl or a group -XR3, in which X is oxygen or sulfur and R3 is C1-C18alkyl, phenyl or C7-C12phenylalkyl, or R2IV is furthermore C3-C18alkenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb ' (IIa) (IIb) in which X1 is C1-C17alkyl, C3-C17alkenyl, C5-C7cycloalkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substi-tuted phenyl, C7-C12phenylalkyl, C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, C1-C10alkylthio or di(C1-C4alkyl)amino and X2 is C1-C18alkyl, C3-C18alkenyl, C5-C7cyclo-alkyl, C1-C4alkyl-substituted C5-C7cycloalkyl, phenyl, C1-C4alkyl- and/or chlorine-substituted phenyl, C7-C12phenylalkyl or C7-C12phenylalkyl which is substituted on the phenyl ring by C1-C4alkyl and/or chlorine, and, if n is 1, Y' is di(C1-C4alkyl)thiocarbamoyl or a group of the formula IIa or IIb, and, if n is 2, Y' is a group IIc or IId, , (IIc) (IId) in which X3 is C1-C12alkylene or phenylene and X4 is C2-C12alkylene or C4-C8alkylene which is interrupted by 1 or 2 oxygen atoms, with the proviso that R2IV and Y' are identical, if R2IV is di(C1-C4alkyl)thio-carbamoyl or a group of the formula IIa or IIb.
15. A compound of the formulae IIIA, IIIB and IIIC according to claim 14, in which R1' is C3-C4alkyl, R2' is C1-C18alkyl, allyl or benzyl and R2"
is C10-C18alkyl or allyl.
is C10-C18alkyl or allyl.
16. A compound of the formula IIID according to claim 14, in which R1" is C1-C4alkyl or phenyl and R2"' is hydroxyl- or C1-C6alkyloxy-substituted C2-C6alkyl .
17. A compound of the formula IIIE according to claim 14, in which n is 1, R1"' is C1-C4alkyl, R2IV is C1-C4alkyl, allyl, benzyl or benzoyl and Y' is di(C1-C4alkyl)thiocarbamoyl or a group IIa or IIb, X1 is C1-C12alkyl, phenyl, dichlorophenyl, C1-C10alkylthio or di(C1-C4alkyl)-amino and X2 is C1-C12alkyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2890/88-9 | 1988-07-29 | ||
| CH289088 | 1988-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1336600C true CA1336600C (en) | 1995-08-08 |
Family
ID=4243898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 606793 Expired - Fee Related CA1336600C (en) | 1988-07-29 | 1989-07-27 | Thiouracils as stabilizers for chlorine-containing polymers |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0354179B1 (en) |
| JP (1) | JPH0288655A (en) |
| CA (1) | CA1336600C (en) |
| DE (1) | DE58908208D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10590311B2 (en) * | 2012-06-27 | 2020-03-17 | Henkel IP & Holding GmbH | Accelerators for two part curable compositions |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE500823C2 (en) * | 1993-01-29 | 1994-09-12 | Whirlpool Europ | Microwave with weighing device |
| DK1325941T3 (en) * | 1995-10-13 | 2005-10-03 | Crompton Vinyl Additives Gmbh | Stabilizer combinations for chlorine-containing polymers |
| MY114466A (en) * | 1996-09-25 | 2002-10-31 | Crompton Vinyl Additives Gmbh | Rigid pvc stabilised with n, n-dimethyl-6-aminouracils |
| ES2196467T3 (en) * | 1998-01-16 | 2003-12-16 | Crompton Vinyl Additives Gmbh | STABILIZER SYSTEM FOR POLYMERS WITH A CHLORINE CONTENT. |
| AU3343899A (en) * | 1998-04-15 | 1999-11-01 | Toshiki Fukuchi | 2-anilinopyrimidinone derivatives, intermediates in the production thereof, process for producing the same and pesticides containing the same as the active ingredient |
| ATE222242T1 (en) * | 1998-06-26 | 2002-08-15 | Crompton Vinyl Additives Gmbh | 6-AMINOURACILE SUBSTITUTED IN THE 5 POSITION AS STABILIZERS FOR HALOGEN-CONTAINING POLYMERS |
| AR023052A1 (en) | 1998-09-25 | 2002-09-04 | Mitsuharu Yoshimura Milton | DERIVATIVES OF PIRIMIDONA |
| ITVA20000023A1 (en) * | 2000-07-19 | 2002-01-19 | Lamberti Spa | HEAT-STABLE PVC COMPOSITIONS. |
| AU2002337498B2 (en) | 2001-09-21 | 2006-08-10 | Mitsubishi Pharma Corporation | 3-substituted-4-pyrimidone derivatives |
| WO2003037888A1 (en) | 2001-09-21 | 2003-05-08 | Mitsubishi Pharma Corporation | 3-substituted-4-pyrimidone derivatives |
| EA009027B1 (en) | 2002-12-16 | 2007-10-26 | Мицубиси Фарма Корпорейшн | 3-substituted-4-pirimidone derivatives |
| TWI357408B (en) | 2003-03-26 | 2012-02-01 | Mitsubishi Tanabe Pharma Corp | 3-substituted-4-pyrimidone derivatives |
| US7892334B2 (en) | 2005-04-12 | 2011-02-22 | Valeo Thermal Systems Japan Corporation | Package of volatile substance and air conditioner for vehicles provided with the package |
| EP3133065A1 (en) | 2015-08-21 | 2017-02-22 | Merck Patent GmbH | Compounds for optically active devices |
| CN106189281A (en) * | 2016-08-09 | 2016-12-07 | 昌吉市新铭泰新型材料科技有限公司 | A kind of production technology of fine Ca-Zn composite heat stabilizer |
| EP3363793A1 (en) | 2017-02-15 | 2018-08-22 | Merck Patent GmbH | Hydrophobic compounds for optically active devices |
| JP2023534254A (en) | 2020-07-15 | 2023-08-08 | エイエムオー・アイルランド | Photoactive device |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE497785A (en) * | ||||
| NL254838A (en) * | 1959-08-14 | 1900-01-01 | ||
| JPS5320061B2 (en) * | 1975-01-31 | 1978-06-24 | ||
| JPS5249260A (en) * | 1975-10-18 | 1977-04-20 | Adeka Argus Chem Co Ltd | Stabilized halogen-containing resin compositions |
| US4105627A (en) * | 1976-09-20 | 1978-08-08 | Argus Chemical Corporation | Mercaptoheterocyclic resin stabilizers |
| JPS5611936A (en) * | 1979-07-11 | 1981-02-05 | Kyodo Yakuhin Kk | Stabilization of chlorine-containing resin |
-
1989
- 1989-07-20 DE DE58908208T patent/DE58908208D1/en not_active Expired - Lifetime
- 1989-07-20 EP EP89810554A patent/EP0354179B1/en not_active Expired - Lifetime
- 1989-07-27 CA CA 606793 patent/CA1336600C/en not_active Expired - Fee Related
- 1989-07-28 JP JP19648189A patent/JPH0288655A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10590311B2 (en) * | 2012-06-27 | 2020-03-17 | Henkel IP & Holding GmbH | Accelerators for two part curable compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0288655A (en) | 1990-03-28 |
| DE58908208D1 (en) | 1994-09-22 |
| EP0354179B1 (en) | 1994-08-17 |
| EP0354179A1 (en) | 1990-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1336600C (en) | Thiouracils as stabilizers for chlorine-containing polymers | |
| US5030671A (en) | Mercaptobenzoates as stabilizers for chlorine-containing polymers | |
| JP3703869B2 (en) | Process for producing hydroxyphenyl-1,3,5-triazine | |
| RU2017719C1 (en) | Method of quadratic acid synthesis | |
| US5071898A (en) | Propane-1,3-dione derivatives and their use as stabilizers for polymers containing chlorine | |
| US4992504A (en) | Ether-containing or thioether-containing 1,3-diketones and the use thereof as stabilizers for chlorine-containing polymers | |
| US4339383A (en) | Imide containing stabilizers for chlorinated thermoplastics | |
| CA1266272A (en) | A 2,2,6,6-tetramethylpiperidine derivative, its production and a stabilizer for synthetic resins containing the same | |
| KR970011575B1 (en) | Piperidyl-triazine derivatives and their use as polymer stabilizers | |
| US4786672A (en) | Anilinotriazines and the use thereof | |
| JP2990364B2 (en) | Substituted aminopyrroles as stabilizers for chlorine-containing polymers | |
| US6790885B2 (en) | Thermally stabilized polyvinyl chloride compositions | |
| US4925944A (en) | Process for the preparation of o-carboxypyridyl- and o-carboxyquinolylimidazolinones | |
| US5288776A (en) | Substituted pyrroles as stabilisers for chlorinated polymers | |
| US5405987A (en) | Process for preparing pyridine and quinoline derivatives | |
| US4567261A (en) | Preparation of riboflavin | |
| US4898900A (en) | 3,3-oxy-bis{[2,2'-di(bromomethyl)]}propanoic acid derivatives | |
| EP0304359A1 (en) | Optically active compound | |
| US2371112A (en) | Dithiobiuret xnd method of | |
| US5177247A (en) | Process for the preparation of hydroxyphenylpropionates | |
| EP1560878B1 (en) | Thermally stabilised pvc compositions | |
| CA2033672C (en) | Melamine derivatives as stabilisers for chlorine-containing polymers | |
| US3207758A (en) | Certain 2-(benzenesulfonamido)-5-alkoxypyrimidines | |
| EP0335262A2 (en) | Phosphite compounds | |
| US4806643A (en) | Preparation of riboflavin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |