CA1113706A - Solid phosphorous acid ester preparations stable to hydrolysis and having an improved stabilizing effect in plastic materials - Google Patents
Solid phosphorous acid ester preparations stable to hydrolysis and having an improved stabilizing effect in plastic materialsInfo
- Publication number
- CA1113706A CA1113706A CA316,970A CA316970A CA1113706A CA 1113706 A CA1113706 A CA 1113706A CA 316970 A CA316970 A CA 316970A CA 1113706 A CA1113706 A CA 1113706A
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- CA
- Canada
- Prior art keywords
- phosphorous acid
- wax
- preparation
- acid ester
- phosphite
- 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.)
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Classifications
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Abstract of the disclosure:
The invention relates to preparations consisting of phosphorous acid esters known as stabilizers for plastic materials and of natural or synthetic waxes. The preparations consist from 20 to 97 weight % of phosphite and from 80 to 3 weight % of wax and they exhibit a better stability to hydro-lysis and a better stabilizing effect than pure phosphites.
The invention relates to preparations consisting of phosphorous acid esters known as stabilizers for plastic materials and of natural or synthetic waxes. The preparations consist from 20 to 97 weight % of phosphite and from 80 to 3 weight % of wax and they exhibit a better stability to hydro-lysis and a better stabilizing effect than pure phosphites.
Description
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- 2 - HOE 77/F 817 The present invention relates to solid phosphorous acid ester preparations stable to hydrolysis and having an improved stabilizing effect in plastics materials.
Phosphorous acid esters gain in importance as anti-oxidants in stabilizing systems for plastic materials, inparticular for the mass products polyethylene, polypropy-lene and polyvinyl chloride. Solid products in the form of powders or scales are preferred to liquid products, owing to the fact that they can be easier dosed and that they are easier misciblenot only with the plastic material, but also with the other components of the total stabilizing composition. However, a weighty disadvantage of these pro-ducts resides in the fact that they h-ydrolyze rapidly in humid air, partially even in the package, during the tran-sport to the consumer and in particular during storageor when the package is opened thereby losing their action as stabilizer. Then the hydrolysis products react with other components of the stabilizing system, such as metal soaps to give insoluble compounds which render the plastic turbid and can even notably disturb or interrupt the production course.
The present invention searchs to surmount these dis-advantages of the solid phosphorous acid esters and to - hinder a hydrolysis thereof or to reduce it considerably, without impairing their efficiency.
Attempts have been made in the past to improve the stability to hydrolysis of phosphorous acid ester stabi-lizers. For example, German Offenlegungsschrift No.
2,626,225 points to the possibility of adding small quan-tities of an amine, proposed at an earlier date. This - ~k . .
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Phosphorous acid esters gain in importance as anti-oxidants in stabilizing systems for plastic materials, inparticular for the mass products polyethylene, polypropy-lene and polyvinyl chloride. Solid products in the form of powders or scales are preferred to liquid products, owing to the fact that they can be easier dosed and that they are easier misciblenot only with the plastic material, but also with the other components of the total stabilizing composition. However, a weighty disadvantage of these pro-ducts resides in the fact that they h-ydrolyze rapidly in humid air, partially even in the package, during the tran-sport to the consumer and in particular during storageor when the package is opened thereby losing their action as stabilizer. Then the hydrolysis products react with other components of the stabilizing system, such as metal soaps to give insoluble compounds which render the plastic turbid and can even notably disturb or interrupt the production course.
The present invention searchs to surmount these dis-advantages of the solid phosphorous acid esters and to - hinder a hydrolysis thereof or to reduce it considerably, without impairing their efficiency.
Attempts have been made in the past to improve the stability to hydrolysis of phosphorous acid ester stabi-lizers. For example, German Offenlegungsschrift No.
2,626,225 points to the possibility of adding small quan-tities of an amine, proposed at an earlier date. This - ~k . .
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- 3 - HOE 77/F 817 procedure has the disadvantages that the stabilizing ac-tion is very brief and that rather inconvenient discolo-rations occur, when using the phosphite treated according to this process, for example in polyvinyl chloride.
The same Offenlegungsschrift recommends the addi-tion of metal salts of organic acids as a more convenient method. However, hydrolysis cannot be prevented by such a procedure. Only following reactions thereof, which become evident in a pH reduction, can be combated. Hence, this method does not exclude the above mentioned sieve obstruc-tion during the plastic processing and a turbidity of the latter.
It has now been found that the hydrolysis of solid phosphorous acid esters can be substantially avoided and in addition that the stabilizing action of these esters in plastic materials can be considerably increased when com-bining them with highly hydrophobic waxes.
The invention, consequently, relates to solid, phos-phorous acid ester preparations stable to hydrolysis and having an improved stabilizing effect in plastic materials, which preparations consist from 20 to 97 ~ by weight of a phosphorous acid ester known per se as stabilizer for plastics and from 80 to 3 % by weight of a wax.
The preparations according to the invention are di-stinguished by an excellent stability to hydrolysis and bythe surprising fact that their stabilizing effect is higher than that of the pure phosphite. This was not to be expected, since the waxes to be added do not have a 29 stabilizing effect in plastics. On the contrary, the con-- .
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The same Offenlegungsschrift recommends the addi-tion of metal salts of organic acids as a more convenient method. However, hydrolysis cannot be prevented by such a procedure. Only following reactions thereof, which become evident in a pH reduction, can be combated. Hence, this method does not exclude the above mentioned sieve obstruc-tion during the plastic processing and a turbidity of the latter.
It has now been found that the hydrolysis of solid phosphorous acid esters can be substantially avoided and in addition that the stabilizing action of these esters in plastic materials can be considerably increased when com-bining them with highly hydrophobic waxes.
The invention, consequently, relates to solid, phos-phorous acid ester preparations stable to hydrolysis and having an improved stabilizing effect in plastic materials, which preparations consist from 20 to 97 ~ by weight of a phosphorous acid ester known per se as stabilizer for plastics and from 80 to 3 % by weight of a wax.
The preparations according to the invention are di-stinguished by an excellent stability to hydrolysis and bythe surprising fact that their stabilizing effect is higher than that of the pure phosphite. This was not to be expected, since the waxes to be added do not have a 29 stabilizing effect in plastics. On the contrary, the con-- .
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- 4 - HOE 77/F 817 tent of phosphite groups acting as stabilizers is reduced by the addition of waxes. It is astonishing that the sta-bilizing action is not reduced as a consequene of this di-lution effect, but that on the contrary an enormous impro-vement of this effect can be observed. Apparently the phos-phorous acid ester and the wax exert a synergistic action.
The improvement of the efficiency of the phosphites of the lnvention combined with waxes applies not only to the processing stability of the plastic but also to its long-duration stability. For example, the reduction of the viscosity occuring when submitting the plastic to a multiple extrusion is retarded considerably when adding to the plastic instead of the pure phosphite an identical quantity by weight of a mixture of wax and phosphite.
The long-duration stability of the plastic is in-fluenced in similar advantageous manner. For example, in this case, the resistance to ageing under heat is improv-ed considerably when adding instead of pure phosphite an identical quantity by weight of the combination of phos-phite and wax.
Hence,,the use of the phosphorous acid ester prepa-rations'according to the invention makes it possible to replace a part of the expensive phosphite by the far less expensive wax, thus even increasing the stabilizing ef-fect.
A further advantage Or the phosphorous acid esterpreparations resides in the fact that their distribution in the plastic material during processing is accelerated.
29 It is quite natural that this effect is ,especially di-1~37~)6 , .~
The improvement of the efficiency of the phosphites of the lnvention combined with waxes applies not only to the processing stability of the plastic but also to its long-duration stability. For example, the reduction of the viscosity occuring when submitting the plastic to a multiple extrusion is retarded considerably when adding to the plastic instead of the pure phosphite an identical quantity by weight of a mixture of wax and phosphite.
The long-duration stability of the plastic is in-fluenced in similar advantageous manner. For example, in this case, the resistance to ageing under heat is improv-ed considerably when adding instead of pure phosphite an identical quantity by weight of the combination of phos-phite and wax.
Hence,,the use of the phosphorous acid ester prepa-rations'according to the invention makes it possible to replace a part of the expensive phosphite by the far less expensive wax, thus even increasing the stabilizing ef-fect.
A further advantage Or the phosphorous acid esterpreparations resides in the fact that their distribution in the plastic material during processing is accelerated.
29 It is quite natural that this effect is ,especially di-1~37~)6 , .~
- 5 - HOE 77/F 817 stinct with high melting phosphite compounds. However, the influence on rather low melting phosphites is advan-tageous as well. It was not to be expected at all that the combination of a wax and a phosphite stabilizer re-sults in a more rapid and more thorough distribution there-of in the plastic.
Finally in some cases a distinct rise of the melting point can be observed when adding a few weight ~ of wax to the phosphite. This effect is surprising, since the melting point of a substance drops generally, as a conse-quence of impurification. The increase of the melting point is especially advantageous when it is intended to use the phosphite for the so-called Bunker stabilization of polyolefin powder. In this process the plastic powder obtained after polymerization has a temperature of from about 60 to 80C. Stabilizer mixtures that contain a low-er melting phosphite, agglomerate at this temperature.
Thus, their homogeneous distribution in the plastic powder is rendered rather difficult. This advantage can be avoided when using phosphites, whose solidification point is increased by adding waxes. A further advantage of these phosphites resides in the fact that they can be easier confectionned by spraying or flaking and that their tendancy to agglomerate under the action of heat and pres-sure is less pronounced than that of untreated phosphites.
Finally, it is surprising that the volatility of thephosphites at elevated temperature is enormously reduced by the addition of waxes or is even completely suppressed : -.
,. ' :' ' : ' ' 1~37~6
Finally in some cases a distinct rise of the melting point can be observed when adding a few weight ~ of wax to the phosphite. This effect is surprising, since the melting point of a substance drops generally, as a conse-quence of impurification. The increase of the melting point is especially advantageous when it is intended to use the phosphite for the so-called Bunker stabilization of polyolefin powder. In this process the plastic powder obtained after polymerization has a temperature of from about 60 to 80C. Stabilizer mixtures that contain a low-er melting phosphite, agglomerate at this temperature.
Thus, their homogeneous distribution in the plastic powder is rendered rather difficult. This advantage can be avoided when using phosphites, whose solidification point is increased by adding waxes. A further advantage of these phosphites resides in the fact that they can be easier confectionned by spraying or flaking and that their tendancy to agglomerate under the action of heat and pres-sure is less pronounced than that of untreated phosphites.
Finally, it is surprising that the volatility of thephosphites at elevated temperature is enormously reduced by the addition of waxes or is even completely suppressed : -.
,. ' :' ' : ' ' 1~37~6
- 6 - HOE 77/F 817 in the case of a rather high portion of wax. This effect is of great importance since it makes sure that in the course of the plastic processing present persons are not exposed to vapors that might be injurious to health.
Known phosphorous acid esters that are suitalbe for the stabilization of plastics include solid, organic phos-phites, for example di-stearylphosphite, tri-stearylphos-phite, preferalby pentaerythritylphosphites as disclosed, for example, in German Offenlegungsschriften Nos.
2,219,695; 2,347,977; 2,621,323; 2,630,257; 2,431,623 and German Patents 1,237,312 and 2,505,152; sugar alcohol phosphites as disclosed in German Offenlegungsschriften Nos. 2,633,392, 2,633,393 and solid triarylphosphites as disclosed in German Offenlegungsschrift 2,606,358. In the case of the latter compounds, the occasional undesir-ed high melting point may be lowered by the addition of waxes and the particularly high tendancy to sublimate at elevated temperature may be reduced as well by this me-thod.
By waxes there are understood products that contain of from 20 to about 500, preferably of from 30 to 250 car-bon atoms in the molecule and that are covered by the ge-neral definition of the term "wax" according to the DGF
standard methods M I1 (75) . ( DGF means the German Society for Fat Investigation). Examples thereof are paraf-fins, for example refined cake paraffins having a melting point in the range from about 40 to about 80C, micropa-raffins, synthetic paraffins having a melting point in the --- ~il37~6
Known phosphorous acid esters that are suitalbe for the stabilization of plastics include solid, organic phos-phites, for example di-stearylphosphite, tri-stearylphos-phite, preferalby pentaerythritylphosphites as disclosed, for example, in German Offenlegungsschriften Nos.
2,219,695; 2,347,977; 2,621,323; 2,630,257; 2,431,623 and German Patents 1,237,312 and 2,505,152; sugar alcohol phosphites as disclosed in German Offenlegungsschriften Nos. 2,633,392, 2,633,393 and solid triarylphosphites as disclosed in German Offenlegungsschrift 2,606,358. In the case of the latter compounds, the occasional undesir-ed high melting point may be lowered by the addition of waxes and the particularly high tendancy to sublimate at elevated temperature may be reduced as well by this me-thod.
By waxes there are understood products that contain of from 20 to about 500, preferably of from 30 to 250 car-bon atoms in the molecule and that are covered by the ge-neral definition of the term "wax" according to the DGF
standard methods M I1 (75) . ( DGF means the German Society for Fat Investigation). Examples thereof are paraf-fins, for example refined cake paraffins having a melting point in the range from about 40 to about 80C, micropa-raffins, synthetic paraffins having a melting point in the --- ~il37~6
- 7 - - HOE 77/F 817 range from 80 to 130C, long chain plant and insect waxes such as carnauba wax, cadelilla wax, partially synthetic ester waxes such as montan wax derivatives, synthetic waxes such as amide waxes, for example distearylethylene-diamide, polyolefin waxes such as polyethylene and polypropylene waxes having a molecular weight in the range of from about 2,000 to 10,000; polyethylene wax oxidates and esters thereof which may be obtained by addition of dialkylphos-phites to long chain ~olefins in the presence of free radical-forming catalysts. Mixtures of said waxes like-wise be used. Preference is given to ethylene polymeriz-ed waxes and amide waxes, in particular to the latter.
The proportion of wax in the wax-phosphorous acid ester preparations according to the invention should be between 3 and 80 ~, preferably between 5 and 40 %, by weight.
The preparations according to the invention are ob-tained preferably in the following manner: The wax and the solid phosphorous acid ester are melted together. Then the molten product is confectioned in known manner, for ex-ample by flaking, spraying, centrifugation or, after,standing, by grinding. It is possible, to addd to the wax-phosphite melt also some components or all components of a total stabilization system such as phenolic antioxi-dants, for example substituted tertiary butylphenols, or-ganic sulfides such as thioglycolic acid esters or di-stearylsulfide; metal sslts of fstty acids, such as stea-rates, laurates, or montanates of calcium, a barium, mag-nesium, cadmium, zinc and lead; light stabilizers such as 29 benzophenones, triazoles or hindered amides. These stabi-.
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The proportion of wax in the wax-phosphorous acid ester preparations according to the invention should be between 3 and 80 ~, preferably between 5 and 40 %, by weight.
The preparations according to the invention are ob-tained preferably in the following manner: The wax and the solid phosphorous acid ester are melted together. Then the molten product is confectioned in known manner, for ex-ample by flaking, spraying, centrifugation or, after,standing, by grinding. It is possible, to addd to the wax-phosphite melt also some components or all components of a total stabilization system such as phenolic antioxi-dants, for example substituted tertiary butylphenols, or-ganic sulfides such as thioglycolic acid esters or di-stearylsulfide; metal sslts of fstty acids, such as stea-rates, laurates, or montanates of calcium, a barium, mag-nesium, cadmium, zinc and lead; light stabilizers such as 29 benzophenones, triazoles or hindered amides. These stabi-.
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- 8 - HOE 77/F 817 lizers often have a wax-like character and are thus capa-ble of intensifying the hydrolysis-avoiding action of the wax. In the case of a total stabilization system there is chosen that individual compound of the series of wax types that guarantees the homogeneity of the melt of the total mixture. This mode of operation has the additional advantage that in a later step all stabilizers may be ad-mixed to the plastic in one operation.
A further possibility of manufacturing the prepara-tions according to the invention consists in coating dis-crete particles of the phosphorous acid ester to be pro-tected with a wax film, for example by applying the wax as melt or dissolved in a solvent onto the phosphite par-ticles prior to or after spraying or flaking the phosphite.
The preparations according to the invention are em- ~ -ployed for the stabilization of plastic compositions bas-ed on polyolefins or chlorine-containing polymers against the detrimental influence of light and heat in an amount of from 0.01 to 5, preferably 0.05 to 2 % by weight, cal-culated on the plastic composition and on the proportion Or phosphorous acid ester in the preparation. Examples of such compositions are those made from polyethylene, preferably polypropylene, copolymers of ethylene and C3-C5 ~ olefins, polyvinylchloride, copolymers thereof with vinylidene chloride and other olefins, chlorinated polyole-fins, and mixtures of polymers.
The following examples illustrate the invention:
E X A M P L E 1: tPreparation Example) 29 a) 2 g Paraffin, melting point from 58 to 60C, are ~ ;' - . .
.
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A further possibility of manufacturing the prepara-tions according to the invention consists in coating dis-crete particles of the phosphorous acid ester to be pro-tected with a wax film, for example by applying the wax as melt or dissolved in a solvent onto the phosphite par-ticles prior to or after spraying or flaking the phosphite.
The preparations according to the invention are em- ~ -ployed for the stabilization of plastic compositions bas-ed on polyolefins or chlorine-containing polymers against the detrimental influence of light and heat in an amount of from 0.01 to 5, preferably 0.05 to 2 % by weight, cal-culated on the plastic composition and on the proportion Or phosphorous acid ester in the preparation. Examples of such compositions are those made from polyethylene, preferably polypropylene, copolymers of ethylene and C3-C5 ~ olefins, polyvinylchloride, copolymers thereof with vinylidene chloride and other olefins, chlorinated polyole-fins, and mixtures of polymers.
The following examples illustrate the invention:
E X A M P L E 1: tPreparation Example) 29 a) 2 g Paraffin, melting point from 58 to 60C, are ~ ;' - . .
.
. :. ~ ' ' 1~37~6
- 9 - HOE 77/F 817 dissolved in 100 ml heptane by boiling. Then after cooling to 80C, 18 g finely ground isophthalic acid di-pentaerythritol phosphite ester, which has been pre-pared according to German Offenlegungsschrift 2,506,207, Example 6, are added while stirring, whereupon the sol-vent is removed at the rotation evaporator at 30C.
b) Analogously to the procedure sub 2), 18 g isophthalic acid pentaerythritol ester are coated with 2 g of a - synthesis paraffin having a melting point of 102C.
c) Analogously to a) 18 g isophthalic acid pentaerythritol ester are coated with 2 g of a cracked-polyethylene wax .
having a chain length of about 200 carbon atoms.
d) Analogously to a) 18 g of acetoacetic acid pentaerythri-tol phosphite ester prepared according to German Aus-legeschrift 2,505,152 are added to a heptane solution containing 2 g of a cracked-polyethylene wax which has a chain length of about 200 carbon atoms, at 60C and the resulting mixture is cooled. The cooled solution is filtered under pressure and concentrated.
e) 20 g Acetoacetic acid pentaerythritol phosphite ester are added while stirring to a melt containing 20 g of a synthesis paraffin having a melting point of 102C.
Then the resulting mixture is cooled.
f) 10 g Di-stearyl-pentaerythrityl diphosphite are added while stirring to a solution of 2 g of triacontylphos-phonic acid methyl ester in heptane which has a tem-perature of about 50C. The solvent is evaporated in - the rotation evaporator at 30C.
29 g) 20 g Di-stearyl-pentaerythrityl diphosphite are added . - .. .. . .- ., ....... :: . . :.: : -. ..... . ...... - .
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b) Analogously to the procedure sub 2), 18 g isophthalic acid pentaerythritol ester are coated with 2 g of a - synthesis paraffin having a melting point of 102C.
c) Analogously to a) 18 g isophthalic acid pentaerythritol ester are coated with 2 g of a cracked-polyethylene wax .
having a chain length of about 200 carbon atoms.
d) Analogously to a) 18 g of acetoacetic acid pentaerythri-tol phosphite ester prepared according to German Aus-legeschrift 2,505,152 are added to a heptane solution containing 2 g of a cracked-polyethylene wax which has a chain length of about 200 carbon atoms, at 60C and the resulting mixture is cooled. The cooled solution is filtered under pressure and concentrated.
e) 20 g Acetoacetic acid pentaerythritol phosphite ester are added while stirring to a melt containing 20 g of a synthesis paraffin having a melting point of 102C.
Then the resulting mixture is cooled.
f) 10 g Di-stearyl-pentaerythrityl diphosphite are added while stirring to a solution of 2 g of triacontylphos-phonic acid methyl ester in heptane which has a tem-perature of about 50C. The solvent is evaporated in - the rotation evaporator at 30C.
29 g) 20 g Di-stearyl-pentaerythrityl diphosphite are added . - .. .. . .- ., ....... :: . . :.: : -. ..... . ...... - .
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- 10 - HOE 77/F 817 while stirring to a melt of 20 g of triacontylphospho-nic acid dimethyl ester. The melt is flaked.
Then each time 18 g di-stearyl-pentaerythritol di-phosphite are melted with h) 2 g synthesis paraffin, melting point 102C or i) 2 g polyethylene wax, having a molar weight of about 2,000 or j) 2 g microparaffin or k) 2 g paraffin having a melting point from 58 to 60C.
The molten products are flaked.
j) 18 g Distearyl-~-hydroxytriacontyl-sorbityl-triphosphite which have been prepared according to German Offenle-gungsschrift 2,633,392, Example 6, are melted with 2 g of a synthesis paraffin having a melting point of 102C.
The melt is sprayed.
m) 18 g Di-stearyl-~-hydroxytriacontyl-sorbityl-triphos-phite are melted with 2 g of a polyolefin wax having a chain length of about 200 carbon atoms. The mixture is flaked.
E X A M P L E 2:
This example is intended to show the improved stabi-lity to hydrolysis of the phosphite preparations according to the invention.
a) 5 g each of the respective samples prepared according to Example 1 are refluxed in 100 ml of demineralized water fcr 20 minutes. The resulting product is filter-ed off while still hot through a folded filter. 40 ml each of the respective samples are withdrawn from the ; 29 aqueous phase and titrated with 0.1 M KOH against bromo-' . . . - : '-' ... .:
.
1~137~
.
Then each time 18 g di-stearyl-pentaerythritol di-phosphite are melted with h) 2 g synthesis paraffin, melting point 102C or i) 2 g polyethylene wax, having a molar weight of about 2,000 or j) 2 g microparaffin or k) 2 g paraffin having a melting point from 58 to 60C.
The molten products are flaked.
j) 18 g Distearyl-~-hydroxytriacontyl-sorbityl-triphosphite which have been prepared according to German Offenle-gungsschrift 2,633,392, Example 6, are melted with 2 g of a synthesis paraffin having a melting point of 102C.
The melt is sprayed.
m) 18 g Di-stearyl-~-hydroxytriacontyl-sorbityl-triphos-phite are melted with 2 g of a polyolefin wax having a chain length of about 200 carbon atoms. The mixture is flaked.
E X A M P L E 2:
This example is intended to show the improved stabi-lity to hydrolysis of the phosphite preparations according to the invention.
a) 5 g each of the respective samples prepared according to Example 1 are refluxed in 100 ml of demineralized water fcr 20 minutes. The resulting product is filter-ed off while still hot through a folded filter. 40 ml each of the respective samples are withdrawn from the ; 29 aqueous phase and titrated with 0.1 M KOH against bromo-' . . . - : '-' ... .:
.
1~137~
.
- 11 - HOE 77/F 817 phenol blue.
The following table indicates the degree of hydro-lysis determined under these conditions, as quotient of the actual consumption of KOH and the theoretically possible consumption of KOH with a complete hydrolysis.
For comparative purposes, the stability to hydrolysis of the basic phosphites of the individual preparations are determined.
Preparation degree of accord. hydrolysis to Ex. consisting of the components (% of the theory) la) 90 % isophthalic acid pentaerythritol phosphite 3.9 10 % paraffin 58/60 lb) 90 % isophthalic acid pentaerythritol phosphite 5.0 10 % synthesis paraffin 1c) 90 % isophtalic acid pentaerythritol phosphite 5.0 lO % polyethylene wax Comp. 100 % isophthalic acid pentaerythritol phosphite 16.0 1g) 50 % di-stearyl-pentaerythrityl-diphosphite 7.0 50 % microparaffin 1h) 90 % di-stearyl-pentaerythrityl-diphosphite 19.0 10 ~ synthesis paraffin li) 90 % di-stearyl-pentaerythrityl-diphosphite 19.0 10 % polyethylene wax 1j) 90 % di stearyl-pentaerythrityl-diphosphite 23.0 10 % microparaffin lk) 90 % di-stearyl-pentaerythrityl-diphosphite 24.0 10 ~ paraffin 58/60 Comp. 100 % di-stearyl-pentaerythrityl-diphosphite 51.0 ll) 90 % di-stearyl-R-hydroxytriacontyl-sorbityl- 4.1 triphosphite 10 % synthesis paraffin 1m) 90 % di-stearyl-~-hydroxytriacontyl-sorbityl- 4.0 triphosphite 10 % polyolefin wax -Comp. 100 % di-stearyl-R-hydroxytriacontyl-sorbityl- 9.0 triphosphite , ' ' " , , "' . ' ' ' ' ', .': - ~ ' .''' , :. . ' ~ "
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The following table indicates the degree of hydro-lysis determined under these conditions, as quotient of the actual consumption of KOH and the theoretically possible consumption of KOH with a complete hydrolysis.
For comparative purposes, the stability to hydrolysis of the basic phosphites of the individual preparations are determined.
Preparation degree of accord. hydrolysis to Ex. consisting of the components (% of the theory) la) 90 % isophthalic acid pentaerythritol phosphite 3.9 10 % paraffin 58/60 lb) 90 % isophthalic acid pentaerythritol phosphite 5.0 10 % synthesis paraffin 1c) 90 % isophtalic acid pentaerythritol phosphite 5.0 lO % polyethylene wax Comp. 100 % isophthalic acid pentaerythritol phosphite 16.0 1g) 50 % di-stearyl-pentaerythrityl-diphosphite 7.0 50 % microparaffin 1h) 90 % di-stearyl-pentaerythrityl-diphosphite 19.0 10 ~ synthesis paraffin li) 90 % di-stearyl-pentaerythrityl-diphosphite 19.0 10 % polyethylene wax 1j) 90 % di stearyl-pentaerythrityl-diphosphite 23.0 10 % microparaffin lk) 90 % di-stearyl-pentaerythrityl-diphosphite 24.0 10 ~ paraffin 58/60 Comp. 100 % di-stearyl-pentaerythrityl-diphosphite 51.0 ll) 90 % di-stearyl-R-hydroxytriacontyl-sorbityl- 4.1 triphosphite 10 % synthesis paraffin 1m) 90 % di-stearyl-~-hydroxytriacontyl-sorbityl- 4.0 triphosphite 10 % polyolefin wax -Comp. 100 % di-stearyl-R-hydroxytriacontyl-sorbityl- 9.0 triphosphite , ' ' " , , "' . ' ' ' ' ', .': - ~ ' .''' , :. . ' ~ "
-. :. ', . ' : :. ' .
' 1~137~)~
- 12 - HOE 77/F 817 b) Water absorption of a phosphorous acid ester prepara-tion according to the invention in comparison with that of the basic phosphorous acid esters when stored in an atmosphere saturated with steam.
Phosphite: Di-stearyl-pentaerythritol di-phosphite Test specimen: circular platelets having a dia-meter of 60 mm and a height of 5 mm 10 Temperature of the air: 20C
Humidity of the air: lOO %
Duration: 24 hours Test Composition of the water absorption No. test specimen in % of the weight of the test specimens __ 2b l lOO % phosphite 10.15 2b 2 70 % phosphite 0.3 30 % cake paraffin 50/60 2b 3 50 % phosphite 0.1 50 % cake paraffin 50/60 2b 4 70 % phosphite *) 1.0 30 % amide wax 2b 5 50 % phosphite 1.0 50 % amide wax 2b 6 70 % phosphite 0.5 30 ~ polyethylene wax 2b 7 50 % phosphite 0,3 50 % polyethylene wax distearoylethylene diamide.
: . :
.
~ -' - .
- 1~137~6
Phosphite: Di-stearyl-pentaerythritol di-phosphite Test specimen: circular platelets having a dia-meter of 60 mm and a height of 5 mm 10 Temperature of the air: 20C
Humidity of the air: lOO %
Duration: 24 hours Test Composition of the water absorption No. test specimen in % of the weight of the test specimens __ 2b l lOO % phosphite 10.15 2b 2 70 % phosphite 0.3 30 % cake paraffin 50/60 2b 3 50 % phosphite 0.1 50 % cake paraffin 50/60 2b 4 70 % phosphite *) 1.0 30 % amide wax 2b 5 50 % phosphite 1.0 50 % amide wax 2b 6 70 % phosphite 0.5 30 ~ polyethylene wax 2b 7 50 % phosphite 0,3 50 % polyethylene wax distearoylethylene diamide.
: . :
.
~ -' - .
- 1~137~6
- 13 - HOE 77/F 817 E X A M P 1, E 3: .
.
This example is intended to show the advantageous rise of the solidification point of the organic phosphi-tes treated according to the invention.
a) Tristearyl-sorbityl-triphosphite prepared according to German Offenlegungsschrift 2,633,393, Example 1 which has a flow point/drop point of 52/53C is mixed in the molten state with 3.5 weight % of a polyethylene oxidate having a drop point of 117C
and an acid number of 19. The cooled product has a flow point/drop point of 86/91C.
b) When melting together tristearyl-sorbityl-triphosphite and 4.5 weight % of a polyethylene oxidate having an acid number of 9 and a drop point of 115C, t,here is ob-tained a preparation having a flow point/drop point of 76/80C.
c) The flow points/drop points of the preparations sub 1h) to 1k) which consist of 90 weight % of di-stearyl-penta-erythritol-diphosphite and 10 weight % of various waxes are determined and compared with that of the pure phos-phite.
Preparation consisting of Flow point / Drop point .:
90 % phosphite 94 / 95 10 ~ synthesis paraffin 90 % phosphite 103 / 104 10 ~ polyethylene wax 90 % phosphite 76.5 / 77 10 % microparaffin 90 % phosphite 62 / 62.5 10 % paraffin 58/60 100 % phosphite 58 / 60 :
: ' ~ ' ' ' . ' ,,,:
, , 1~37~6 ,,
.
This example is intended to show the advantageous rise of the solidification point of the organic phosphi-tes treated according to the invention.
a) Tristearyl-sorbityl-triphosphite prepared according to German Offenlegungsschrift 2,633,393, Example 1 which has a flow point/drop point of 52/53C is mixed in the molten state with 3.5 weight % of a polyethylene oxidate having a drop point of 117C
and an acid number of 19. The cooled product has a flow point/drop point of 86/91C.
b) When melting together tristearyl-sorbityl-triphosphite and 4.5 weight % of a polyethylene oxidate having an acid number of 9 and a drop point of 115C, t,here is ob-tained a preparation having a flow point/drop point of 76/80C.
c) The flow points/drop points of the preparations sub 1h) to 1k) which consist of 90 weight % of di-stearyl-penta-erythritol-diphosphite and 10 weight % of various waxes are determined and compared with that of the pure phos-phite.
Preparation consisting of Flow point / Drop point .:
90 % phosphite 94 / 95 10 ~ synthesis paraffin 90 % phosphite 103 / 104 10 ~ polyethylene wax 90 % phosphite 76.5 / 77 10 % microparaffin 90 % phosphite 62 / 62.5 10 % paraffin 58/60 100 % phosphite 58 / 60 :
: ' ~ ' ' ' . ' ,,,:
, , 1~37~6 ,,
- 14 - HOE 77/F 817 E X A M P L E 4:
This example is intended to show the improved effi-ciency of the phosphite preparations according to the in-vention as compared to that of the basic phosphites. It can be seen from the measured values that with the prepa-rations according to the invention both the ageing stabi-lity under heat and the processing stability are consi-derably improved and that the phosphite content is in all cases lower than that in the comparative tests.
a) Examination of the ageing stability under heat A mixture of 100 parts by weight of unstabilized polypropylene powder having a density of 0.90 (melt index about 6 g/10 minutes determined according to ASTM D t238-62 T) and 0.15 part by weight of 3',5'-di-tertiary butyl-4'-hydroxy-phenyl-propionic acid octadecyl ester and ; 0.1 part by weight each of the respective phosphite or of the phosphite preparation is homoge-nized for five minutes at 200C on a two roll mill. The plastic melt is molded at 200C into a rough sheet of 1 mm thickness.
Strip specimens of 60 x 10 x 1 mm are punched out from the sheet and are then suspended in a heating cabinet with air circulation on a moter driven stand with rotating trays. The samples are submitted 29 to a uniformous temperature treatment of . , ~ .. . ..
. . - . . . - , . . . . -- ': ' . .' "' .'' : ', ' "' ,, ' ' .. . .
.3706
This example is intended to show the improved effi-ciency of the phosphite preparations according to the in-vention as compared to that of the basic phosphites. It can be seen from the measured values that with the prepa-rations according to the invention both the ageing stabi-lity under heat and the processing stability are consi-derably improved and that the phosphite content is in all cases lower than that in the comparative tests.
a) Examination of the ageing stability under heat A mixture of 100 parts by weight of unstabilized polypropylene powder having a density of 0.90 (melt index about 6 g/10 minutes determined according to ASTM D t238-62 T) and 0.15 part by weight of 3',5'-di-tertiary butyl-4'-hydroxy-phenyl-propionic acid octadecyl ester and ; 0.1 part by weight each of the respective phosphite or of the phosphite preparation is homoge-nized for five minutes at 200C on a two roll mill. The plastic melt is molded at 200C into a rough sheet of 1 mm thickness.
Strip specimens of 60 x 10 x 1 mm are punched out from the sheet and are then suspended in a heating cabinet with air circulation on a moter driven stand with rotating trays. The samples are submitted 29 to a uniformous temperature treatment of . , ~ .. . ..
. . - . . . - , . . . . -- ': ' . .' "' .'' : ', ' "' ,, ' ' .. . .
.3706
- 15 - HOE 77/F 817 140C in a controlled atmosphere while supplying a definite quantity of fresh air.
The time is measured after which a begin-ning local embrittlement can be observed at several positions. This phenomenon is characterized according to the German in-dustrial standard DIN 53,383 by the forma-tion of discolored, turbid, partially flak-ing-off zones. This period, expressed in days, is indicated in the following table.
b) Examination of the processing stability The mixture described sub a) is used to determine its melt index (i2/300) prior to and after a thermal stress at 300C for a period of 60 minutes. The de-; 15 termined melt indices are listed in the following table as the quotiert i prior. The smaller this quo-i after tient, the higher the thermal decomposition of the plastic melt and the lower its processing stability.
' ' ..
~37q~
The time is measured after which a begin-ning local embrittlement can be observed at several positions. This phenomenon is characterized according to the German in-dustrial standard DIN 53,383 by the forma-tion of discolored, turbid, partially flak-ing-off zones. This period, expressed in days, is indicated in the following table.
b) Examination of the processing stability The mixture described sub a) is used to determine its melt index (i2/300) prior to and after a thermal stress at 300C for a period of 60 minutes. The de-; 15 termined melt indices are listed in the following table as the quotiert i prior. The smaller this quo-i after tient, the higher the thermal decomposition of the plastic melt and the lower its processing stability.
' ' ..
~37q~
- 16 - HOE 77/F 817 phosphite according Ageing resistance Processing stability to Example under heat i prior to 1a) (da56ys) 0.173 1b) 62 0.195 1c) 65 0.184 isophthalic acid dipentaerythri- 48 0.160 tol phosphite ester (Comp.) 1d) 63 0.234 le) 61 0.185 acetoacetic acid pentaerythritol 44 0.147 phosphite ester (Comp.) 1f) 57 0.227 1g) 51 0.218 di-stearylpentaerythrityl-di- 43 0.144 phosphite (Comp.) E X A M P L E 5:
This example is intended to show that the volatility of phosphites is reduced with the addition of waxes accord-ing to the present invention.
- For this purpose 1 g each of the respective phosphite is melted together with 2 g polyethylene wax having a molar weight of from 2,000 to 3,000. Then a precisely weighed quantity of th~is mixture is stored in a heating cabinet for two hours at 200C at the air and then the mixture is weighed again.
The following table summarizes the determined volati-lities and the flow points/drop points compared to that of the starting phosphites.
' - . :
. ~ : . -: ' :
. : ,:
~ 1~137~)6 .
This example is intended to show that the volatility of phosphites is reduced with the addition of waxes accord-ing to the present invention.
- For this purpose 1 g each of the respective phosphite is melted together with 2 g polyethylene wax having a molar weight of from 2,000 to 3,000. Then a precisely weighed quantity of th~is mixture is stored in a heating cabinet for two hours at 200C at the air and then the mixture is weighed again.
The following table summarizes the determined volati-lities and the flow points/drop points compared to that of the starting phosphites.
' - . :
. ~ : . -: ' :
. : ,:
~ 1~137~)6 .
- 17 - HOE 77/F 817 phosphite or phosphite Flow / Drop Volatility wax mixture point point (weight %) tris-(2,4-di-tert.-butyl- 180 29.8 phenyl)-phosphite dto. with 2 parts poly-152/156 1.23 ethylene wax di-stearyl-pentaerythri-55/ 60 6.85 tyl diphosphite dto. with 2 parts poly-114/115 0.92 ethylene wax di-stearyl-~-hydroxytri-75/ 78 10.9 acontylsorbityl-triphos-phite dto. with 2 parts poly- 114/115 0.24 ethylene wax ~.
,
,
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A solid phosphorous acid ester preparation stable to hydrolysis and having an improved stabilizing effect in plastic materials, comprising from 20 to 97 weight % of a known, solid organic phosphorous acid ester stabilizer for a plastic material, selected from the group consisting of di-stearylphosphite, tri-stearylphosphite, pentaerythritylphosphites, sugar alcohol phos-phites and solid triaryl phosphites, and from 80 to 3 weight % of a wax selected from the group consisting of natural or parti-ally synthetic ester waxes, amide waxes, esters of polyolefinwax oxidates and wax-like esters of long chain phosphonic acids.
2. A preparation as claimed in claim 1 in which other components of a stabilizing system are added thereto.
3. A preparation as claimed in claim 2 in which the other components of the stabilizing system are selected from the group of sulfidic and phenolic antioxidants, metal salts of fatty acids, light stabilizers selected from the group consisting of benzophenones, benzotriazoles and hindered amines.
4. A process for the preparation of the solid phosphorous acid ester preparation as defined in claim 1 in which, either a) the phosphorous acid ester and the wax are melted together and the melt is confectioned in known manner to give flakes, granules or powders, or b) the wax is applied onto the particles of the phosphorous acid in the form of a melt or dissolved in a solvent.
5. A process for the stabilization of plastic material selected from the group of polyolefins and cholrine-containing polymers, against the detrimental influence of light and heat, which comprises adding to the polymer a stabilizing preparation as defined in claim l in an amount of from 0.01 to 5 weight %, calculated on the polymer and the proportion of phosphite in the stabilizer preparation.
6. A process as claimed in claim 5 in which further stabilizers are added to the plastic material.
7. A plastic material selected from the group of polyolefins and chlorine-containing polymers containing a preparation as claimed in claim 1, claim 2 or claim 3, in an amount of from 0.01 to 5 % by weight, calculated on the phosphorous acid ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2753136.8 | 1977-11-29 | ||
| DE2753136A DE2753136B2 (en) | 1977-11-29 | 1977-11-29 | Solid phosphorous acid ester preparations with an improved stabilizing effect in plastics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1113706A true CA1113706A (en) | 1981-12-08 |
Family
ID=6024859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA316,970A Expired CA1113706A (en) | 1977-11-29 | 1978-11-28 | Solid phosphorous acid ester preparations stable to hydrolysis and having an improved stabilizing effect in plastic materials |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0002243B1 (en) |
| JP (1) | JPS5483951A (en) |
| AT (1) | AT368769B (en) |
| AU (1) | AU522136B2 (en) |
| BR (1) | BR7807807A (en) |
| CA (1) | CA1113706A (en) |
| DE (2) | DE2753136B2 (en) |
| ES (1) | ES475321A1 (en) |
| IT (1) | IT1101440B (en) |
| NO (1) | NO783997L (en) |
| ZA (1) | ZA786674B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1120793A (en) * | 1977-12-23 | 1982-03-30 | Ved K. Sahajpal | Encapsulated phosphites |
| US4402858A (en) * | 1982-04-14 | 1983-09-06 | Uniroyal, Inc. | Hydrolytically stable antioxidant composition |
| FR2647800A1 (en) * | 1989-05-31 | 1990-12-07 | Organo Synthese Ste Fse | Tris(2,4-di-tert-butylphenyl) phosphite having improved physical properties |
| DE102008020442A1 (en) | 2008-04-23 | 2009-10-29 | Merck Patent Gmbh | pigment preparations |
| DE102008064202A1 (en) | 2008-12-22 | 2010-06-24 | Merck Patent Gmbh | pigment granules |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1131943B (en) * | 1960-11-21 | 1962-06-20 | Deutsche Ges Schaedlingsbek | Moisture-protected metal phosphide |
| DE1768283B1 (en) * | 1968-04-25 | 1971-02-25 | Hoechst Ag | Process for the production of thermally stable carboxamides and their use as lubricants in plastics processing |
| US3666700A (en) * | 1970-12-03 | 1972-05-30 | Exxon Research Engineering Co | Polyvinyl chloride composition |
| US3755200A (en) * | 1972-02-14 | 1973-08-28 | Emery Industries Inc | Liquid stabilizer system for polyvinyl chloride |
| NL7506988A (en) * | 1975-06-12 | 1976-12-14 | Akzo Nv | ORGANIC TRIPHOSCYCLES WITH IMPROVED HYDROLYTIC STABILITY. |
-
1977
- 1977-11-29 DE DE2753136A patent/DE2753136B2/en not_active Withdrawn
-
1978
- 1978-11-23 ES ES475321A patent/ES475321A1/en not_active Expired
- 1978-11-25 DE DE7878101457T patent/DE2861885D1/en not_active Expired
- 1978-11-25 EP EP78101457A patent/EP0002243B1/en not_active Expired
- 1978-11-27 IT IT30238/78A patent/IT1101440B/en active
- 1978-11-28 CA CA316,970A patent/CA1113706A/en not_active Expired
- 1978-11-28 AT AT0850078A patent/AT368769B/en not_active IP Right Cessation
- 1978-11-28 JP JP14612978A patent/JPS5483951A/en active Pending
- 1978-11-28 BR BR7807807A patent/BR7807807A/en unknown
- 1978-11-28 NO NO783997A patent/NO783997L/en unknown
- 1978-11-28 ZA ZA00786674A patent/ZA786674B/en unknown
- 1978-11-28 AU AU41981/78A patent/AU522136B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2753136B2 (en) | 1981-04-02 |
| IT7830238A0 (en) | 1978-11-27 |
| AU522136B2 (en) | 1982-05-20 |
| IT1101440B (en) | 1985-09-28 |
| NO783997L (en) | 1979-05-30 |
| DE2753136A1 (en) | 1979-06-07 |
| DE2861885D1 (en) | 1982-07-22 |
| EP0002243B1 (en) | 1982-06-02 |
| BR7807807A (en) | 1979-07-31 |
| AU4198178A (en) | 1979-06-07 |
| ZA786674B (en) | 1979-11-28 |
| ES475321A1 (en) | 1979-04-01 |
| EP0002243A1 (en) | 1979-06-13 |
| ATA850078A (en) | 1982-03-15 |
| AT368769B (en) | 1982-11-10 |
| JPS5483951A (en) | 1979-07-04 |
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