CA1180476A - Chlorinated thermoplastics stabilised with aminouracils - Google Patents
Chlorinated thermoplastics stabilised with aminouracilsInfo
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- CA1180476A CA1180476A CA000403542A CA403542A CA1180476A CA 1180476 A CA1180476 A CA 1180476A CA 000403542 A CA000403542 A CA 000403542A CA 403542 A CA403542 A CA 403542A CA 1180476 A CA1180476 A CA 1180476A
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- aminouracil
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- moulding composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to thermoplastic moulding compositions based on vinyl chloride polymers and containing, as stabiliser, 0.1 to 5 % by weight of all aminouracil of the formula I
(I)
(I)
Description
Case 3-13414/CGM 262/~
.. ..
Chlorinated thermoplastics stabilised with aminouracils The presen~ invention relates to chlorinated thermoplastics wlich are stabilised with aminouracils, and to the use of specific aminouracils for stabilising such subs~rates.
The use of aminouracils as stabilisers for PVC, in particular of 1,3-dimethyl-6-aminouracil and 1,3-dimethyl-6-anilinouracil, is known from German Auslegeschrift 1 694 873. It has been found, however;
that these known stabilisers for PVC do not always satisfy the exacting demands of actual practicc. Their effectiveness, i.e. their compatibility with the substrate~
is insufficient. For example, 1,3-dimethyl-6-aminouracil gives rise to pronounced haze in moulding compounds stabilised therewith. It is the object of the present invention to provide stabilisers which do not have these shortcomings.
Accordingly~ the present invention provides thermo-plastic moulding compositions based on vinyl chloride polymers, which compositions contain 0.1 to 5 % by weight of an aminouracil of the formula I
o .
7~
-- 2 ~
wherein Rl is hydrogen and R and R3 are C2-C4alkyl.
The most preferred aminouracils are 1,3-diethyl-6-aminouracil or L,3-di-n-butyL-6 aminouracil.
The uracils employed in the practice of this invention are known and may be obtained by known methods, eOg. as described in US patent specification 2 598 936.
Those compounds which are novel can be prepared by methods analogous to known ones, e.g. as described in the US patent specification just referred to.
The uracils employed in the practice of this invention are most suitable for protecting chlorinated thermoplastics against hea~-induced degradation. They may be incorporated in the thermoplastics to be stabilised singly or in admixture with one another, before processing in conventional apparatus, and in respective amounts of 0.1 to 5 % by weight, preferably of 0.2 to 1D5 % bY weight, based on the entire composition~
A still better stabilising action is obtained by additionally using customary amounts of one of ~he conventional PVC stabilisers and/or additives such as epoxy compounds~ preferably epoxidised fatty acid esters such as epoxidised soybean oil, phosphites, organometal compounds of metals of the second main and auxiliary group of the Periodic Table, e.g. metal carboxylates or metal ~' ~
~ .
7~
phenolates, in particular metal salts of carboxylic acids contalning 8 to 20 carbon atoms or of phenols containing 6 to 20 carbon atoms, e.g calcium stearate or zinc stearate, or also inorganic salts of metals of the second auxiliary group of the Periodic Table, e.g. ~nC12, as well as organotin compounds, in particular mixtures of mono- and diorganotin compounds, such as mono-n-octyl tris-isooctyl thioglycolate and di-n-octyl bis-isooctyl thioglycolate, or organoantimony compounds SUCIl as antimony tris-isooctyl thioglycolate (isooctyl = L,1~3,3-tetramethylbutyl).
Co-stabilisers are preferably incorporated in amounts of 0.05 to 6 % by weight, preferably 0.1 to 3 % by weight, based on the entire composition. The ratio of aminouracil to co-stabiliser may be from 2:1 to 1:8.
Particularly suitable conventional phosphites are those of the general formulae II, III or IV
R O--~OR ( I I ) OR
8 ~ 5 ( I I I ) R5~P/ 2\C/ 2 ~OR5 (IV) wherein each of R5, R6 and R7 independently of one another is Cl-C18alkyl, Cl-C20alkenyl, C6-C12aryl, C7-cl9alkar which is unsubstituted or substituted by hydroxy or cl-C4alkoxy, or is C5 C7cycloalkyl, and R~ is C2-C6alkylene 7~
which is unsubstituted or substituted by Cl-C18alkyl, C2-C13alkoxymethyl or C2~C13alkylthiomethyl or by phenyl, or is C6-ClOarylene which is unsubstltuted or substituted by Cl-C4alkyl, or is C5-C7cycloalkylene.
~ , R and R as Cl-C18alkyl are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl,n-hexyl, n-octyl, n-nonyl, decyl, dodecyl, tetradecyl~ hexadecyl or octadecyl. Alkyl groups containing 8 to 18 carbon atoms Qre preferred, R5, ~6 and R7 as Cl-C20alkenyl are e.g. allyl~
but-2.-enyl~ pentenyl, hexenyl~ heptenyl or oleyl.
R , R and R7 as aryl may be e.g. naphthylg biphenyl or, preferably, phenyl.
R , R and R as C7~Clgalkaryl which is unsubstituted or substituted by hydroxy or Cl-C~alkoxy are e g~ tolyl, ethylphenyl~ xylyl, cumyl, cymyl, cresyl, 4-methoxyphenyl~
.. ..
Chlorinated thermoplastics stabilised with aminouracils The presen~ invention relates to chlorinated thermoplastics wlich are stabilised with aminouracils, and to the use of specific aminouracils for stabilising such subs~rates.
The use of aminouracils as stabilisers for PVC, in particular of 1,3-dimethyl-6-aminouracil and 1,3-dimethyl-6-anilinouracil, is known from German Auslegeschrift 1 694 873. It has been found, however;
that these known stabilisers for PVC do not always satisfy the exacting demands of actual practicc. Their effectiveness, i.e. their compatibility with the substrate~
is insufficient. For example, 1,3-dimethyl-6-aminouracil gives rise to pronounced haze in moulding compounds stabilised therewith. It is the object of the present invention to provide stabilisers which do not have these shortcomings.
Accordingly~ the present invention provides thermo-plastic moulding compositions based on vinyl chloride polymers, which compositions contain 0.1 to 5 % by weight of an aminouracil of the formula I
o .
7~
-- 2 ~
wherein Rl is hydrogen and R and R3 are C2-C4alkyl.
The most preferred aminouracils are 1,3-diethyl-6-aminouracil or L,3-di-n-butyL-6 aminouracil.
The uracils employed in the practice of this invention are known and may be obtained by known methods, eOg. as described in US patent specification 2 598 936.
Those compounds which are novel can be prepared by methods analogous to known ones, e.g. as described in the US patent specification just referred to.
The uracils employed in the practice of this invention are most suitable for protecting chlorinated thermoplastics against hea~-induced degradation. They may be incorporated in the thermoplastics to be stabilised singly or in admixture with one another, before processing in conventional apparatus, and in respective amounts of 0.1 to 5 % by weight, preferably of 0.2 to 1D5 % bY weight, based on the entire composition~
A still better stabilising action is obtained by additionally using customary amounts of one of ~he conventional PVC stabilisers and/or additives such as epoxy compounds~ preferably epoxidised fatty acid esters such as epoxidised soybean oil, phosphites, organometal compounds of metals of the second main and auxiliary group of the Periodic Table, e.g. metal carboxylates or metal ~' ~
~ .
7~
phenolates, in particular metal salts of carboxylic acids contalning 8 to 20 carbon atoms or of phenols containing 6 to 20 carbon atoms, e.g calcium stearate or zinc stearate, or also inorganic salts of metals of the second auxiliary group of the Periodic Table, e.g. ~nC12, as well as organotin compounds, in particular mixtures of mono- and diorganotin compounds, such as mono-n-octyl tris-isooctyl thioglycolate and di-n-octyl bis-isooctyl thioglycolate, or organoantimony compounds SUCIl as antimony tris-isooctyl thioglycolate (isooctyl = L,1~3,3-tetramethylbutyl).
Co-stabilisers are preferably incorporated in amounts of 0.05 to 6 % by weight, preferably 0.1 to 3 % by weight, based on the entire composition. The ratio of aminouracil to co-stabiliser may be from 2:1 to 1:8.
Particularly suitable conventional phosphites are those of the general formulae II, III or IV
R O--~OR ( I I ) OR
8 ~ 5 ( I I I ) R5~P/ 2\C/ 2 ~OR5 (IV) wherein each of R5, R6 and R7 independently of one another is Cl-C18alkyl, Cl-C20alkenyl, C6-C12aryl, C7-cl9alkar which is unsubstituted or substituted by hydroxy or cl-C4alkoxy, or is C5 C7cycloalkyl, and R~ is C2-C6alkylene 7~
which is unsubstituted or substituted by Cl-C18alkyl, C2-C13alkoxymethyl or C2~C13alkylthiomethyl or by phenyl, or is C6-ClOarylene which is unsubstltuted or substituted by Cl-C4alkyl, or is C5-C7cycloalkylene.
~ , R and R as Cl-C18alkyl are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl,n-hexyl, n-octyl, n-nonyl, decyl, dodecyl, tetradecyl~ hexadecyl or octadecyl. Alkyl groups containing 8 to 18 carbon atoms Qre preferred, R5, ~6 and R7 as Cl-C20alkenyl are e.g. allyl~
but-2.-enyl~ pentenyl, hexenyl~ heptenyl or oleyl.
R , R and R7 as aryl may be e.g. naphthylg biphenyl or, preferably, phenyl.
R , R and R as C7~Clgalkaryl which is unsubstituted or substituted by hydroxy or Cl-C~alkoxy are e g~ tolyl, ethylphenyl~ xylyl, cumyl, cymyl, cresyl, 4-methoxyphenyl~
2,4-dimethoxyphenyL, alkoxyphenyl or butoxyphenyL
R , ~ and R7 as C5-C7cycloalkyl are e.g. cyclopentyl, cycloheptyl and, in particular, cyclohexyl.
As C2-C6alkylene which is unsubstituted or substitut-ed by Cl-C18alkyl or phenyl, R may be e.g. ethylene, propyl-ene or hexamethylene, substituted by methyl, ethyl, propyl isopropyl, butyl, hexyl, decyl, dodecyl, tetradecyl, octadecyi or phenyl, and is, in particular, 2-propyl 2-methylpropylenP, l-propyl 2-ethylpropylene, phenylethylene, or also unsubstituted ethylene.
,~ ,.~
As C2-C6alkylene substituted by C2-C13alkoxymethyl or C2-cl3a~ylthiome~y~ R may be e.g. ethoxymethylethylene, butoxyme~hylethylene~ octyloxymethyletllylene or dodecylthio-methylethylene.
As C6-ClOarylene which is unsul)stituted or substitut-ed by Cl-C4alkyl~ R is e.g. tert-butylphenylene or unsubstituted phenylene.
As C5-C7cycloalkylene, R8 is in particular cyclohexylene~
Preferred phospllites of the formula IV are those in which R5 is Cl-C18alkyl and, in particular, C8-C18alkyl, and is most preferably octyl or decyl, Very suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl or tricyclohexyl phosphite. Especially preferred phosphites are a-ryl-dialkyl phosphites and alkyl-diaryl phosphites, e.g, phenyldidecyl phosphite, nonylphenyldidecyl phosphite, (2,4-di-tert-butylphenyl)-didodecyl phosphite and (2,6-di-tert-butylphenyl)-didodecyl phosphite.
A particularly good stabilising action is obtained by adding to t~e aminouracils of the formula I at least one epoxy compound and/or metal carboxylate or metal phenolate of a metal of the second main group of the Pe.iodic Table, preferably a calcium carboxylate, most preferably calcium stearate. A still better stabilising action is obtained by using additionally at least one æinc or cadmium carboxylate, organotin compound or organoantimony compound. Preferred organotin compounds are mixtures of mono- and diorganotin compounds.
7~
The best stabilising action, however~ is obtained by stabilising the chLorinated theremoplastics with a mixture of at least one aminouracil of the formula I, a~
least one epoxy compound and/or metal carboxylate or metal phenolate of a metal oE the second main group of the Periodic Table, at least one zinc or cadmium carboxylate or organotin compound, and at least one of the phosphites defined above.
Surp~-isingl~, even a relativel~ small concentration of an aminoura~il of the formula I ensures an excellent stabilising action under these conditions.
It is preferred to use vinyl chloride polymers or copolymers for the moulding co;npositions of the invention.
Suspension and mass polymers, and emulsion polymers having a low content of emulsifier, are preferred. Examples of suitable comonomers for the copolymers are: vinyl acetate, vinylidene chLoride, trans-dichloroethane~ ethylene, propylene, butylene, maleic acid, acrylic acid, fumeric acid or itaconic acid. Further suitable chlorlnated polymers are post-chlorinated PVC and chlorinated olefins, as well as graft polymers of PVC with EVA and MBS~
The thermoplastics stabi]ised according to the invention are obtained by incorporating the stabilisers and, if desired, further stabilisers, in the p~lymer. A
homogeneous mixture of stabiliser and polyvinyl chloride can be obtained e.g. using a two-roll mixer ln the temperature range from 150 to 210 C. Depending on the end use of the moulding compound~ further additives may also be incorporated before or simultaneously with the incorporation of the stabiliser. Exampl~es of further additives are: lubrlcants (preferably montan waxes or glycerol esters), fatty acid esters, paraffins, plasticisers, ~, ~V~ t~
fillers, carbon black, asbestos, kaolin, talcumg glass fi~res~ modifiers (suc~ as impact strength additives) 3 fluorescent whitening agents, pigments, light stabillsers, W absorbers, flame retardan~s, antistats or further co-sta~ilisers, e g. antioxidants, in particular phenolic ant;oxidants, The thermoplastic moulding compositions obtained according to the invention can be processed to moulded articles by conventional moulding methods, e~g.
by extrusion, injection moulding or calendering. The use of the moulding compositions as plastisols is also possible.
The stabilisers employed in the practice of this invention effect excellent stabilisation of the thermoplastic moulding compositions obtained. The light stability is also good.
The invention is illustrated in more detail by the following Examples, in which parts are by weight, unless otherwise stated~
Exa~ A dry blend comprising each of the ~ormul.at.ions lîsted bel.ow in 1) - le) is rolled for 5 minutes at 180C
on a mixer roll~ Test samples having a thickness o~
0.3 mm are then ta'~en from the rolled sheet obtained. These samples are subjected to heat in an oven at 180C, and at 10 minute intervals the thermal ageing of a sanple is determined according to the Yellowness Index of ASTM D 1925-70.
The results are reported in the ~ollowing tables.
1) S-PVC (K-value 64)100 parts epoxidised soybean oil2 parts Static heat test (180C) Therm~ ageing (min) o lo 1 20 Yellowness Index 28,080,0 7100 la) S-PVC (K-value 64) 100 parts epoxidised soybean oil 2 parts 1,3 diethyl-6-aminouracil 0.6 part Static heat test (180C) ¦Thermal ageing (min) ¦ ¦ lo ~ 20 ¦ 30 ¦ 40 ¦ 50 ¦
_ _ Yellowness Index 3,8 6~7 9,5 17,9 29 52.9 ~'"''~``
7~
g lb) S-PVC (K-value 64) 100 parts epoxidised soybean oil 2 parts lg3-di-n butyl~6-aminouracil 0.6 part Static heat test (180C) Thermal ageing (min) o ¦ lo 20 30 40 _ _. ~ _ Yellowness Index 2~5 ~ 6~3 14J7 24,6 52, , _ _ .
lc) S-PVC (K-value 64) 100 parts epoxidised soybean oil 3 parts zinc stearate 0~15 part calcium stearate 0,35 part tridecyl phosphite 0.55 part Static heat test (180 C) _ _ I __ Thermal ageing (min) o lo ¦ 20 ` 30 40 _ _ , Yellowness Index 25~ 2 33.7 33,7 69,8 ~loo ïd) S-PVC (K-value 64) loo parts epoxidised soybean oil 3 parts 1,3-di-ethyl-6-aminouracil 0.46 part zinc stearate 0.15 part calcium stearate 0.35 part tridecyl phosphite 0.55 part Static heat test (180C) -- 10 ~
. _ _I~
IThermal ageing (min) o lo 20 30 40 _ _ Yellowness Index ¦ 2,3 6,0 9,5 14,7 29,4 le) S-PVC (K-value 64) 100 parts epoxi.dised soybean oil 3 parts 1,3-di-n-butyl-6-aminouracil 0.6 part zinc stearate 0.15 part calcium stearate 0~35 part tridecyl phosphite 0.55 part Static heat test (180C) ___ Tho~ ~1 ,~eir~ Inin) o lo 20 30 ¦ 40 _ . I ._ ¦Y~llowness Index 2,4 407 7t6 14,9 J 44,0 Exam~ 2: A dry blend consisting of 100 parts of S-PVC
(K-value 64), 2 parts of epoxidised soybean oil and 0.6 part of one of the aminouracils listed in the following table, is rolled for 5 minutes at loOC on a mixer roll. The rolled sheet obta.ined is processed at 180C or 1 minute to 1 mm sheetS (panels) which are visually assessed for haze. The results are reported in the following table.
1,3-diethyl-6-aminouracil no haze _ . .
1,3-di-n-butyl-6-aminouracil no haze 7~
Examele 3: A dry blend consisting of 100 parts of S-PVC ~-value 64), 2 parts of epoxidised soybean oil and 0.46 part of 1,3-diethyl-6-aminouracil is rolled for 5 minutes at 180C pn a mixer roll. The rolled sheet so ob~ained is processed a~ 180C for 1 minute to 1 mm sheets (panels). The degree of yellowing determined in accordance with the Yellownes Index of ASTM D 1925-70 is 16.5.
Example 4: A dry blend consisting of 100 parts of S-PVC ~-value 64), 2 parts of epoxidised soybean oil and 0.6 part of 1,3-di-n-butyl-6-aminouracil is processed to 1 mm sheets (panels) as described in Example 3. The degree of yellowing determined in accordance with the Yellowness Index of ASTM D 1925-70 is 15.9.
Example 5: A dry blend consisting of 100 parts of S-PVC ~-value 64), 3 parts of epoxidised soybean oil, 0.46 part of 1,3-diethyl-6-aminouracil, 0.15 part of zinc stearate, 0.35 parts of calcium stearate and 0.55 part of tridecyl phosphite, is processed to 1 mm sheets ~panels) as described in ~xample 3. The degree of yellowing determined in accordance with the Yellowness Index of ASTM D 1925-70 is 13.9.
Exam~e 6: A dry blend consisting of 100 parts of S-PVC (K-value 64), 3 parts of epoxidised soybean oil, 0 6 part of 1~3~di-n-butyl-6-aminouracil, 0.15 part of zinc stearate, 0.35 parts of calcium stearate and 0.55 part of tridecyl phosphite, is processed ~o 1 mm sheets ;~
,~, '7~i (panels) as described in Example 3. The degree of yellowing determined in accordance with the Yellowness Inclex of ASTM D 1925-70 is 14.1.
A sheet having a degree of yellowing of 64.9 (determined in accordance with the Yellowness Index of ASTM D 1925-70) is obtained with a dry blend as described in Examples 5 and 6, but without the addition of aminouracil.
!: ; ',
R , ~ and R7 as C5-C7cycloalkyl are e.g. cyclopentyl, cycloheptyl and, in particular, cyclohexyl.
As C2-C6alkylene which is unsubstituted or substitut-ed by Cl-C18alkyl or phenyl, R may be e.g. ethylene, propyl-ene or hexamethylene, substituted by methyl, ethyl, propyl isopropyl, butyl, hexyl, decyl, dodecyl, tetradecyl, octadecyi or phenyl, and is, in particular, 2-propyl 2-methylpropylenP, l-propyl 2-ethylpropylene, phenylethylene, or also unsubstituted ethylene.
,~ ,.~
As C2-C6alkylene substituted by C2-C13alkoxymethyl or C2-cl3a~ylthiome~y~ R may be e.g. ethoxymethylethylene, butoxyme~hylethylene~ octyloxymethyletllylene or dodecylthio-methylethylene.
As C6-ClOarylene which is unsul)stituted or substitut-ed by Cl-C4alkyl~ R is e.g. tert-butylphenylene or unsubstituted phenylene.
As C5-C7cycloalkylene, R8 is in particular cyclohexylene~
Preferred phospllites of the formula IV are those in which R5 is Cl-C18alkyl and, in particular, C8-C18alkyl, and is most preferably octyl or decyl, Very suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl or tricyclohexyl phosphite. Especially preferred phosphites are a-ryl-dialkyl phosphites and alkyl-diaryl phosphites, e.g, phenyldidecyl phosphite, nonylphenyldidecyl phosphite, (2,4-di-tert-butylphenyl)-didodecyl phosphite and (2,6-di-tert-butylphenyl)-didodecyl phosphite.
A particularly good stabilising action is obtained by adding to t~e aminouracils of the formula I at least one epoxy compound and/or metal carboxylate or metal phenolate of a metal of the second main group of the Pe.iodic Table, preferably a calcium carboxylate, most preferably calcium stearate. A still better stabilising action is obtained by using additionally at least one æinc or cadmium carboxylate, organotin compound or organoantimony compound. Preferred organotin compounds are mixtures of mono- and diorganotin compounds.
7~
The best stabilising action, however~ is obtained by stabilising the chLorinated theremoplastics with a mixture of at least one aminouracil of the formula I, a~
least one epoxy compound and/or metal carboxylate or metal phenolate of a metal oE the second main group of the Periodic Table, at least one zinc or cadmium carboxylate or organotin compound, and at least one of the phosphites defined above.
Surp~-isingl~, even a relativel~ small concentration of an aminoura~il of the formula I ensures an excellent stabilising action under these conditions.
It is preferred to use vinyl chloride polymers or copolymers for the moulding co;npositions of the invention.
Suspension and mass polymers, and emulsion polymers having a low content of emulsifier, are preferred. Examples of suitable comonomers for the copolymers are: vinyl acetate, vinylidene chLoride, trans-dichloroethane~ ethylene, propylene, butylene, maleic acid, acrylic acid, fumeric acid or itaconic acid. Further suitable chlorlnated polymers are post-chlorinated PVC and chlorinated olefins, as well as graft polymers of PVC with EVA and MBS~
The thermoplastics stabi]ised according to the invention are obtained by incorporating the stabilisers and, if desired, further stabilisers, in the p~lymer. A
homogeneous mixture of stabiliser and polyvinyl chloride can be obtained e.g. using a two-roll mixer ln the temperature range from 150 to 210 C. Depending on the end use of the moulding compound~ further additives may also be incorporated before or simultaneously with the incorporation of the stabiliser. Exampl~es of further additives are: lubrlcants (preferably montan waxes or glycerol esters), fatty acid esters, paraffins, plasticisers, ~, ~V~ t~
fillers, carbon black, asbestos, kaolin, talcumg glass fi~res~ modifiers (suc~ as impact strength additives) 3 fluorescent whitening agents, pigments, light stabillsers, W absorbers, flame retardan~s, antistats or further co-sta~ilisers, e g. antioxidants, in particular phenolic ant;oxidants, The thermoplastic moulding compositions obtained according to the invention can be processed to moulded articles by conventional moulding methods, e~g.
by extrusion, injection moulding or calendering. The use of the moulding compositions as plastisols is also possible.
The stabilisers employed in the practice of this invention effect excellent stabilisation of the thermoplastic moulding compositions obtained. The light stability is also good.
The invention is illustrated in more detail by the following Examples, in which parts are by weight, unless otherwise stated~
Exa~ A dry blend comprising each of the ~ormul.at.ions lîsted bel.ow in 1) - le) is rolled for 5 minutes at 180C
on a mixer roll~ Test samples having a thickness o~
0.3 mm are then ta'~en from the rolled sheet obtained. These samples are subjected to heat in an oven at 180C, and at 10 minute intervals the thermal ageing of a sanple is determined according to the Yellowness Index of ASTM D 1925-70.
The results are reported in the ~ollowing tables.
1) S-PVC (K-value 64)100 parts epoxidised soybean oil2 parts Static heat test (180C) Therm~ ageing (min) o lo 1 20 Yellowness Index 28,080,0 7100 la) S-PVC (K-value 64) 100 parts epoxidised soybean oil 2 parts 1,3 diethyl-6-aminouracil 0.6 part Static heat test (180C) ¦Thermal ageing (min) ¦ ¦ lo ~ 20 ¦ 30 ¦ 40 ¦ 50 ¦
_ _ Yellowness Index 3,8 6~7 9,5 17,9 29 52.9 ~'"''~``
7~
g lb) S-PVC (K-value 64) 100 parts epoxidised soybean oil 2 parts lg3-di-n butyl~6-aminouracil 0.6 part Static heat test (180C) Thermal ageing (min) o ¦ lo 20 30 40 _ _. ~ _ Yellowness Index 2~5 ~ 6~3 14J7 24,6 52, , _ _ .
lc) S-PVC (K-value 64) 100 parts epoxidised soybean oil 3 parts zinc stearate 0~15 part calcium stearate 0,35 part tridecyl phosphite 0.55 part Static heat test (180 C) _ _ I __ Thermal ageing (min) o lo ¦ 20 ` 30 40 _ _ , Yellowness Index 25~ 2 33.7 33,7 69,8 ~loo ïd) S-PVC (K-value 64) loo parts epoxidised soybean oil 3 parts 1,3-di-ethyl-6-aminouracil 0.46 part zinc stearate 0.15 part calcium stearate 0.35 part tridecyl phosphite 0.55 part Static heat test (180C) -- 10 ~
. _ _I~
IThermal ageing (min) o lo 20 30 40 _ _ Yellowness Index ¦ 2,3 6,0 9,5 14,7 29,4 le) S-PVC (K-value 64) 100 parts epoxi.dised soybean oil 3 parts 1,3-di-n-butyl-6-aminouracil 0.6 part zinc stearate 0.15 part calcium stearate 0~35 part tridecyl phosphite 0.55 part Static heat test (180C) ___ Tho~ ~1 ,~eir~ Inin) o lo 20 30 ¦ 40 _ . I ._ ¦Y~llowness Index 2,4 407 7t6 14,9 J 44,0 Exam~ 2: A dry blend consisting of 100 parts of S-PVC
(K-value 64), 2 parts of epoxidised soybean oil and 0.6 part of one of the aminouracils listed in the following table, is rolled for 5 minutes at loOC on a mixer roll. The rolled sheet obta.ined is processed at 180C or 1 minute to 1 mm sheetS (panels) which are visually assessed for haze. The results are reported in the following table.
1,3-diethyl-6-aminouracil no haze _ . .
1,3-di-n-butyl-6-aminouracil no haze 7~
Examele 3: A dry blend consisting of 100 parts of S-PVC ~-value 64), 2 parts of epoxidised soybean oil and 0.46 part of 1,3-diethyl-6-aminouracil is rolled for 5 minutes at 180C pn a mixer roll. The rolled sheet so ob~ained is processed a~ 180C for 1 minute to 1 mm sheets (panels). The degree of yellowing determined in accordance with the Yellownes Index of ASTM D 1925-70 is 16.5.
Example 4: A dry blend consisting of 100 parts of S-PVC ~-value 64), 2 parts of epoxidised soybean oil and 0.6 part of 1,3-di-n-butyl-6-aminouracil is processed to 1 mm sheets (panels) as described in Example 3. The degree of yellowing determined in accordance with the Yellowness Index of ASTM D 1925-70 is 15.9.
Example 5: A dry blend consisting of 100 parts of S-PVC ~-value 64), 3 parts of epoxidised soybean oil, 0.46 part of 1,3-diethyl-6-aminouracil, 0.15 part of zinc stearate, 0.35 parts of calcium stearate and 0.55 part of tridecyl phosphite, is processed to 1 mm sheets ~panels) as described in ~xample 3. The degree of yellowing determined in accordance with the Yellowness Index of ASTM D 1925-70 is 13.9.
Exam~e 6: A dry blend consisting of 100 parts of S-PVC (K-value 64), 3 parts of epoxidised soybean oil, 0 6 part of 1~3~di-n-butyl-6-aminouracil, 0.15 part of zinc stearate, 0.35 parts of calcium stearate and 0.55 part of tridecyl phosphite, is processed ~o 1 mm sheets ;~
,~, '7~i (panels) as described in Example 3. The degree of yellowing determined in accordance with the Yellowness Inclex of ASTM D 1925-70 is 14.1.
A sheet having a degree of yellowing of 64.9 (determined in accordance with the Yellowness Index of ASTM D 1925-70) is obtained with a dry blend as described in Examples 5 and 6, but without the addition of aminouracil.
!: ; ',
Claims (10)
1. A thermoplastic moulding composition based on a vinyl chloride polymer, which composition contains 0.1 -to 5 %
by weight of an aminouracil of the formula (I) wherein R1 is hydrogen and R2 and R3 are C2-C4alkyl.
by weight of an aminouracil of the formula (I) wherein R1 is hydrogen and R2 and R3 are C2-C4alkyl.
2. A moulding composition according to claim 1, wherein the aminouracil is 1,3-di-n-butyl-6-aminouracil.
3. A moulding composition according to claim 1, wherein the aminouracil is 1,3-diethyl-6-aminouracil.
4. A moulding composition according to claim 1, which additionally contains one or more conventional PVC stabilisers and/or additives selected from the group consisting of epoxy compounds, phosphites, organometal compounds of metals of the second main and auxiliary group of the Periodic Table, inorganic salts of metals of the second auxiliary group of the Periodic Table, and organotin compounds or organoantimony compounds.
5. A moulding composition according to claim 4, which contains, as conventional additional ingredient, at least one epoxy compound and/or a metal carboxylate or metal phenolate of a metal of the second main group of the Periodic Table.
6. A moulding composition according to claim 4, which contains, as conventional additional ingredient, at least one phosphite.
7. A moulding composition according to claim 5, which additionally contains at least one phosphite.
8. A moulding composition according to claim 5, which additionally contains at least one zinc or cadmium carboxylate or organotin compound.
9. A moulding composition according to claim 8, which additionally contains at least one phosphite.
10. A method of stabilising vinyl chloride polymers, which comprises incorporating therein an aminouracil according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH344081 | 1981-05-26 | ||
| CH3440/81-0 | 1981-05-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1180476A true CA1180476A (en) | 1985-01-02 |
Family
ID=4256000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000403542A Expired CA1180476A (en) | 1981-05-26 | 1982-05-21 | Chlorinated thermoplastics stabilised with aminouracils |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0065934B1 (en) |
| JP (1) | JPS57200436A (en) |
| CA (1) | CA1180476A (en) |
| DE (1) | DE3265213D1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5859100A (en) * | 1996-09-25 | 1999-01-12 | Ciba Specialty Chemicals Corporation | Rigid PVC stabilised with N,N-dimethyl-6-aminouracils |
| US6156830A (en) * | 1998-06-26 | 2000-12-05 | Witco Vinyl Additives Gmbh | 5-substituted 6-aminouracils as stabilizers for halogenated polymers |
| AU2003203275B2 (en) * | 1995-10-13 | 2004-12-02 | Chemtura Vinyl Additives Gmbh | Stabiliser combinations for chlorine-containing polymers |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE59010370D1 (en) | 1989-10-06 | 1996-07-18 | Ciba Geigy Ag | Stabilized chlorine-containing polymer compositions |
| EP0433230B1 (en) | 1989-12-11 | 1997-05-14 | Ciba SC Holding AG | Beta-ketoesters as stabilizers for chlorine containing polymerisates |
| ATE224423T1 (en) * | 1995-10-13 | 2002-10-15 | Crompton Vinyl Additives Gmbh | STABILIZER COMBINATIONS FOR CHLORINE-CONTAINING POLYMERS |
| EP0930332B1 (en) * | 1998-01-16 | 2003-05-14 | Crompton Vinyl Additives GmbH | Stabiliser system for polymers containing chlorine |
| EP1510545A3 (en) * | 1998-06-26 | 2005-06-15 | Wolfgang Dr. Wehner | 1,3 substituted 6-aminouraciles to stabilize halogenated polymers |
| ES2189300T3 (en) * | 1998-06-26 | 2003-07-01 | Crompton Vinyl Additives Gmbh | NEW 6-AMINOURACILOS MODIFIED WITH NH2 AS STABILIZERS FOR HALOGENED POLYMERS. |
| BE1012673A3 (en) * | 1999-05-10 | 2001-02-06 | Solvay | Novel 6-amino-uracil, preparation and use. |
| JP4516650B2 (en) * | 2000-01-21 | 2010-08-04 | 水澤化学工業株式会社 | Stabilizer composition for chlorine-containing polymer |
| EP1318168A1 (en) * | 2001-12-04 | 2003-06-11 | Crompton Vinyl Additives GmbH | Stabiliser combinations for chlorinated polymers |
| EP1426406A1 (en) * | 2002-12-02 | 2004-06-09 | Crompton Vinyl Additives GmbH | Monosubstituted 6-aminouracils for stabilizing halogenated polymers |
| PL2013279T3 (en) | 2006-05-02 | 2010-09-30 | Basf Se | Derivatives of pyrimidines as flame retardants |
| CN101437886B (en) * | 2006-05-02 | 2011-11-09 | 西巴控股有限公司 | Derivatives of pyrimidines as flame retardants |
| WO2008075510A1 (en) * | 2006-12-21 | 2008-06-26 | Mizusawa Industrial Chemicals, Ltd. | Stabilizer for chlorinated polymer and chlorinated-polymer composition |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1694873C3 (en) * | 1966-02-12 | 1973-11-08 | Ciba-Geigy Marienberg Gmbh, 6140 Marienberg | Stabilization of vinyl chloride polymers |
-
1982
- 1982-05-21 CA CA000403542A patent/CA1180476A/en not_active Expired
- 1982-05-21 EP EP82810218A patent/EP0065934B1/en not_active Expired
- 1982-05-21 DE DE8282810218T patent/DE3265213D1/en not_active Expired
- 1982-05-26 JP JP57089588A patent/JPS57200436A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003203275B2 (en) * | 1995-10-13 | 2004-12-02 | Chemtura Vinyl Additives Gmbh | Stabiliser combinations for chlorine-containing polymers |
| US5859100A (en) * | 1996-09-25 | 1999-01-12 | Ciba Specialty Chemicals Corporation | Rigid PVC stabilised with N,N-dimethyl-6-aminouracils |
| US6156830A (en) * | 1998-06-26 | 2000-12-05 | Witco Vinyl Additives Gmbh | 5-substituted 6-aminouracils as stabilizers for halogenated polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57200436A (en) | 1982-12-08 |
| EP0065934B1 (en) | 1985-08-07 |
| EP0065934A1 (en) | 1982-12-01 |
| DE3265213D1 (en) | 1985-09-12 |
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