CA2092952A1 - Dispersions of polymer additives in fatty acid esters - Google Patents
Dispersions of polymer additives in fatty acid estersInfo
- Publication number
- CA2092952A1 CA2092952A1 CA 2092952 CA2092952A CA2092952A1 CA 2092952 A1 CA2092952 A1 CA 2092952A1 CA 2092952 CA2092952 CA 2092952 CA 2092952 A CA2092952 A CA 2092952A CA 2092952 A1 CA2092952 A1 CA 2092952A1
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- CA
- Canada
- Prior art keywords
- polymer
- phase comprises
- fatty acid
- stable dispersion
- continuous phase
- 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.)
- Abandoned
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
Abstract
DISPERSIONS OF POLYMER ADDITIVES
IN FATTY ACID ESTERS
Abstract of the Invention Stable dispersions of polymer stabilizers in a normally liquid fatty acid ester of a polyhydric organic compound are provided. These dispersions can be advantageously employed to uniformly distribute the stabilizer throughout a polymer resulting in improved polymer properties.
IN FATTY ACID ESTERS
Abstract of the Invention Stable dispersions of polymer stabilizers in a normally liquid fatty acid ester of a polyhydric organic compound are provided. These dispersions can be advantageously employed to uniformly distribute the stabilizer throughout a polymer resulting in improved polymer properties.
Description
- 1 - 2~ 3 3~
DISPERSIONS OF POLYMER ADDITIVES
IN F~TT~ ~CI~ ESTE~$ _ Field of the Invention The present invention relates to dispersions of polymer additives in a continuous liquid phase.
More particularly, the present invention relates to the distribution of a dispersion of solid additives throughout polymeric compositions, especially thermoplastic polymers.
Bakqround of the Invention Stabilizers are commonly combined with polymers for various purposes including the prevention of thermal, oxidative and/or photo-degradation of the polyrner during fabrication, processing, storage and end use. The effectiveness of the stabilizer in performing its intended purpose is a function of how uniformly mixed or dispersed the stabilizer is within the polymer. Areas containing low levels of stabilizer can degrade more rapidly than ar~as containing higher levels of the stabilizer. In many instances the stabilizers are solids which melt at high temperatures and are difficult to disperse throughout the polymer. This inability to disperse the stabilizer often reduces the overall performance of the polymer.
A number of procedures well known to the art have been used to incorporate stabilizers and other additives into polymer systems. For example, high shear mixing is frequently employed. To obtain acceptable dispersion, this method requires application of high shear forces for extended periods - 2 - 2~
of time to raise the temperature of the polymer to form a molten material. Since many stabilizers have significantly higher melting temperatures than the polymer, the additives do not melt and are often distributed non-uniformly in the polymer.~ E~posure of the polymer to high temperatures during high shear mi~ing can result in polymer degradation.
Another method is melt e~trusion by which the stabilizer is distributed in the polymer as it is being e~truded through a die. While this method operates at lower temperatures and therefore does not cause polymer degradation to the same extent as high shear mi~ing, this technique does not adequately distribute small levels of stabilizers uniformly in the resin. Melt e~trusion tends to be useful primarily for mi~ing large quantities of materials homogeneously.
Accordingly, a need exists to distribute stabilizers uniformly throughout a polymer without subjecting the polymer to conditions which might induce polymer degradation.
Summary nf ~he Inventio~
The present invention provides particular stable dispersions of polymer stabilizers. The dispersions comprise a normally liquid fatty acid ester of a polyhydric organic compound as the liquid or continuous phase. The discrete phase of the dispersion is a stabilizer. The present invention also provides a method for uniformly distributing polymer stabilizers throughout polymeric compositions, such as polyolefins.
DISPERSIONS OF POLYMER ADDITIVES
IN F~TT~ ~CI~ ESTE~$ _ Field of the Invention The present invention relates to dispersions of polymer additives in a continuous liquid phase.
More particularly, the present invention relates to the distribution of a dispersion of solid additives throughout polymeric compositions, especially thermoplastic polymers.
Bakqround of the Invention Stabilizers are commonly combined with polymers for various purposes including the prevention of thermal, oxidative and/or photo-degradation of the polyrner during fabrication, processing, storage and end use. The effectiveness of the stabilizer in performing its intended purpose is a function of how uniformly mixed or dispersed the stabilizer is within the polymer. Areas containing low levels of stabilizer can degrade more rapidly than ar~as containing higher levels of the stabilizer. In many instances the stabilizers are solids which melt at high temperatures and are difficult to disperse throughout the polymer. This inability to disperse the stabilizer often reduces the overall performance of the polymer.
A number of procedures well known to the art have been used to incorporate stabilizers and other additives into polymer systems. For example, high shear mixing is frequently employed. To obtain acceptable dispersion, this method requires application of high shear forces for extended periods - 2 - 2~
of time to raise the temperature of the polymer to form a molten material. Since many stabilizers have significantly higher melting temperatures than the polymer, the additives do not melt and are often distributed non-uniformly in the polymer.~ E~posure of the polymer to high temperatures during high shear mi~ing can result in polymer degradation.
Another method is melt e~trusion by which the stabilizer is distributed in the polymer as it is being e~truded through a die. While this method operates at lower temperatures and therefore does not cause polymer degradation to the same extent as high shear mi~ing, this technique does not adequately distribute small levels of stabilizers uniformly in the resin. Melt e~trusion tends to be useful primarily for mi~ing large quantities of materials homogeneously.
Accordingly, a need exists to distribute stabilizers uniformly throughout a polymer without subjecting the polymer to conditions which might induce polymer degradation.
Summary nf ~he Inventio~
The present invention provides particular stable dispersions of polymer stabilizers. The dispersions comprise a normally liquid fatty acid ester of a polyhydric organic compound as the liquid or continuous phase. The discrete phase of the dispersion is a stabilizer. The present invention also provides a method for uniformly distributing polymer stabilizers throughout polymeric compositions, such as polyolefins.
- 3 - 2~9~
Petailed pe~ription of the Invention By the teachings of this present invention, stable dispersions of polymer stabilizers are provided using normally li~uid fatty acid esters of polyhydric organic compounds as the liquid or continuous phase of the dispersion. The stable dispersions of the invention can be distributed uniformly in various polymers, and with particular advantage in thermoplastics, by blending the dispersion and polymer by a variety of mixing techniques known in the art including melt extrusion.
The liquid or continuous phase of the dispersions of this invention comprises a normally liquid, at ambient conditions, fatty acid ester of a polyhydric organic compound. The fatty acids from which the esters are derivable can be saturated or ethylenically unsaturated and usually have from 12 to 18 carbon atoms. The preferred class of polyhydric compounds, in turn, from which the fatty acid esters are derivable consist of carbon, hydrogen and oxygen and contain from three to six hydroxyl groups which can be the terminal hydroxyl groups of etho~ylated moieties. Oxygen can also be present as the cyclic ether group, I
H-C~
¦ O, in which event the polyhydric H-C/
I
alcohol has no more than four hydroxyl groups.
Oxygen can also be present in the polyhydric alcohol as acyclic ether linkages such as in the --4-- 2 0 ~
aforementioned hydroxyl-terminated ethogylated or poly(o~yethylene) moieties. It is to be understood that the fatty acid ester can contain zero or from one to si~ hydro~yl-terminated poly(ogyethylene) chains. When the ester does contain such chains, i.e., -(OC2H4)n-OH, the total average number (n) Of o~yethylene units in the ester is a positive number, usually ranging from about 1 to about 100. The continuous phase of the dispersions of this invention may comprise any combination of the aforesaid types of fatty acid esters.
Most preferably the continuous phase of the dispersions contain fatty acid esters of sorbitan, glycerol or mixtures thereof. Illustrative of suitable sorbitan and glyceryl esters are sorbitan monooleate, sorbitan monolaurate, sorbitan trioleate, glyceryl trioleate, glyceryl monooleate, and the like. Various sorbitan esters, such as sorbitan monooleate and sorbitan monolaurate, are available commercially as Span 80 a~d Span 20 respectively from Imperial Chemical Industries Ltd. (ICl). Similarly, various glyceryl esters are commercially available from Witco Corporation. Poly(o~yethylene)-containing or ethoxylated derivatives of the sorbitan or glyceryl esters can also be used in the present invention. The latter materials are also commercially available from ICI, such as for e~ample, Tween 20. Of the above ester compositions, especially preferred as the continuous phase of the dispersions of this invention are sorbitan monooleate, sorbitan monolaurate and glyceryl trioleate.
2~9~ ~i2 The continuous phase of the dispersion may also contain other liquids which are miscible in the fatty acid esters of the polyhydric organic compound. Preferably, the second liqui~ of the continuous phase also improves the properties of the polymer. Illustrative liquids include, but are not limited to, processing aids, liquid stabilizers and lubricants. Liquid stabilizers include organomodified silicones such as hindered amine silicones, including W SIL~ 299 (Enichem Co.).
Especially preferred organomodified silicones are polyether silicone processing aids such as VCARSIL~
PA-l (Union Carbide Chemicals and Plastics Company Inc.) The above-described fatty acid esters of polyhydric coumpounds are known to be useful as lubricants and surface active agents. Therefore, their use as the continuous phase of the dispersions of this invention allows for the elimination or reduction in the concentration of other additives for such purposes.
Improved performance of a polymer is noted as the stabilizers become more uniformly distributed within the polymer becomes more uniform. In particular, color and resistance to thermal degradation improve as stabilizers, such as antio~idants are more uniformly dispersed within the polymer. Illustrative of but not limited to then types of stabilizers which can be used in the present invention are ultraviolet light stabilizers, thermostabilizers, antioxidants, catalyst deactivators and acid neutralizers. Stabilizers are D-16~99 important additives because of their ability to modify overall polymer performance. Because of their high cost relative to the cost of most polymers, it is essential that staoilizers are uniformly distributed throughout the polymer to realize ma~imum benefit.
As used herein, the term "stabilizer" is meant to include all materials which can be added to polymer compositions for the purpose of improving or retaining the polymer's properties under various conditions of exposure and use. Although many stabilizers are solids, liquid stabilizers can also be employed in the present invention. The better the dispersion of the stabilizer in the polymer, the better the stabilizer efficiency. Stabilizers contain polar moieties and often are particularly troublesome to disperse into relatively non-polar polymer resins, particularly polyolefin resins. For e~ample, the use of ETHANOX~ 330, a relatively high molecular weight and high melting (244C) antioxidant, in polypropylene and nylon theoretically offers high performance, but has been excluded from many applications because of the difficulty in obtaining uniform additive-resin dispersions. For similar reasons, relatively polar zinc oxide, a low-cost acid scavenger, also is not used routinely for stabilizing polyolefins because it is difficult to disperse uniformly. ~ore particularly, the present invention provides a solution to the problems associated with attempts to disperse polar additives into non-polar polymers.
Specific e~amples of the stabilizers component of the dispersions of this invention D~16899 - 7 - 2~3~ J
include: fatty amine, fatty amide antistatic agents and catalyst deactivators such as KEMAMINE~ and XEMAMIDE~ and ATMER~ 163 (witco Chemical Co.);
stabilizers including organic phosphites, and other organic phosphorus compounds, such as tri-n-dodecylphosphite, the bis-substituted pentaerythritol diphosphites such as bis~2,4-di-t-butylphenyl) pentaerythritol diphosphite, tris(mono-and di-nonylphenyl)phosphite IRGAFOS~ 168 (Ciba -Geigy); phosphonites including fluorophosphonites such as ETHANOX~ 398 (Ethyl Corp) and SANDOSTAB~
P-EPQ ~Sandoz); hindered phenols, such as octadecyl 3-(3',5'-di-t-butyl-4-hydro~yphenyl)- propionate, IONOL~ (Shell), TOPANOL~CA (ICI); IRGANOX~
antio~idants such as IRGANOX~ 1076, 1093, 1098 and IRGANOX~ 1010 (tetrakis[methylene-3(3'-5'-di-tert-butyl-4'hydro~yphenyl)propionate] methane) (Ciba-Geigy); and the ETHANOX~ antio~idants such as ETHANOX~ 330 (1,3,5-tri-methyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) benzene) and ETHANOX~ 702 (Ethyl Corp.); and ISONOX~ 129 (2,2'-ethylidene-bis(4,6-di-t-butyl)phenol) (Schenectady Chemical); the CYANOX~ antioxidants including CYANOX~ 1790 (American Cyanamid); the GOOD-RITE~ antioxidants including GOODRITE~ 3114 (B.F. Goodrich Chemical Co.); antio~idants/metal deactivators, such as the NAUGARD9 products such as NAUGARD~ XLl (Uniroyal Inc.) and IRGANOX~ MD 1024 (Ciba-Geigy); thiodipropionate stabilizers such as dilauryl thiodipropionate; hindered amine compounds such as those containing tetra alkyl-piperidinyl functionality, including the light stabilizers and W
- ~ - 2~3~v~
absorbers such as TIN W IN~ 149, TIN WIN~ 326 and 327, TIN W IN~ P, TIN W IN~ 622LD (Ciba-Geigy), CYANOX~ 3346 (American Cyanamid), GOO~RITE~ 304~ (B.F. Goodrich Chemical Co.); benzophenone stabilizers, such as CYASORB~- W 2098 (American Cyanamid), W INUL~M 90 and W INUL~ 490 (BASF); blends of organic phosphorus compounds and hindered phenol antioxidants including IRGANOX~ 1411, 1412, 501W, 712FF, B-225, B-215, and 900 (Ciba-Geigy); nucleating agents such as dibenzilydene sorbitol; acid neutralizers including metal o~ides such as zinc oxide; hydrotalcites; metal stearates; calcium lactate and the like.
The concentration of the dispersion, i.e., the weight of the discrete phase (stabilizer) in the liquid phase, is usually about 0.1 to about 80 percent by weight, generally about 1 to about 60 percent by weight and usually about 10 to about 50 percent by weight.
The dispersions of this invention are prepared by admixing the stabilizer with the normally liquid fatty ester of a polyhydric organic compound by using a high shear mi~er such as a COWLES~ mi~er.
Also within the scope of this invention are mi~tures of solid and liquid stabilizers as the discrete phase of the dispersion.
The process of the present invention can be used for dispersing the various polymer stabilizers in a wide variety of thermoplastic systems. The process can be advantageously employed with homopolymers, copolymers and polymer blends.
Illustrative of, but not limited to the polymers include polyolefins, such as high density 2 ~ r,; ~j ~
polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene, polyesters, polyvinyl chloride, polyacrylates, polystyrene, styrene-butadiene copolymers, polyvinyl chloride/polyvinylacetate copolymers, ethylene/
acrylic acid copolymers, ethylene/acrylic acid/vinyl acetate terpolymers and the like.
Stabilizers which are used to formulate the dispersions of this invention generally have the following particle size distribution: at least about 95% by weight of the particles have a diameter of less than 150 microns and about 20 percent by weight have a particle size of less than about 20 microns.
Preferably at least about 95~ by weight of the particles have a diameter of less than 100 microns and at least 35% by weight have a particle size of less than 10 microns. Even more preferable are stabilizers having an average particle size of less than 20 microns and more than 50% by weight less than 10 microns.
Particularly desirable for purposes of this invention are stabilizers having the particle size described above which are comprised of a bimodal size distribution. A bimodal distribution has two separate peaks around which the particles are clustered. Especially advantageous are those bimodal distributions where the weight fraction of the larger particles, relative to the smaller particles, is from about 30 to about 90 percent of the total weight of the particles and the ratio of the average particle size of the larger particle size is at least two and preferably from about 2 to about 100. The _ lo - 2~ 3~
dispersions having this particle size and weight distributions have been found to be not only e~tremely stable but also have a lower viscosity compared to dispersions only containing smal~er particles.
While not wishing to be bound by any specific theory, it is believed that the stability of the dispersions of this invention is due to the occurrence of controlled agglomeration. Controlled agglomeration is believed to result in a structure which extends through the whole li~uid volume and supports the individual particles, preventing the particles from settling. Consequently, there is no need to incorporate e~traneous ingredients in the dispersion, such as surfactants and the like, whose sole purpose is to ensure the stability of the dispersion.
As used throughout this specification, which includes the claims, ~stable dispersions" are those wherein there is less than about 5 percent by volume separation of the liguid phase, evidenced by the formation of a two-phase system, after centrifugation of the dispersions under a force of one-hundred times the force of gravity (lOOG) for one hour.
Particularly desirable are those dispersions which exhibit less than about 5 percent by volume separation after centrifugation under a force of 1400G for 9 hours. Dispersions which exhibit less than about 5 percent by volume separation after centrifugation under a force of 1400G for 4 hours are considered as stable, under ambient conditions, for at least 6 months. As used herein the phrase dispersion also encompasses suspensions and emulsions.
2 ~ J
The dispersion containing the desired stabilizer in dispersed form is added directly to the thermoplastic resin which can be in either the form of solid particles (in pellet, granule, powder, etc., form) or in the molten state. In other words, the stable dispersions of the present invention can be pre-blended with polymer particles before polymer processing operations such as melt e~trusion, injection molding and the like, or the dispersion can be added directly to a molten polymer during its processing. The compounding of the dispersion and thermoplastic resin may be done by spraying or by mixing or tumbling the resin and suspension in a ribbon blender, utilizing a two-roll mill, an e~truder, including single screw and multiple screw e~truders, a Banbury (Farrel Corp.) or Brabender mixer. Suitable procedures and equipment will readily occur to those skilled in the art of polymer processing. Concentrates or master batches of the dispersion and resin may be produced and blended with virgin resin such as on a mill before final processing. The rolls on a two-roll mill may operate at different speeds and temperatures. In spite of the simplicity of the milling operation, extrusion is usually preferred for blending the suspension and resin since an e~truder can operate continuously, for example to produce strands that may be cut by a rotating knife to produce pellets.
The stable dispersion can be added to the synthetic resin at the end of the resin manufacturing process, such as directly after resin polymerization or polycondensation, for example while it is still ~ ~3 ~ 2 t~
molten or to powdered or pelleted polymer particles.
However, it also is possible, and often more convenient, to admix the dispersion with the synthetic resin subsequently during one of its myriad processing stages, for e~ample prior to or during extrusion. Using a fluid dispersion not only facilitates the mixing/dispersing of the additive with the polymer, but also makes it easier to control the amount of stabilizer mixed with the resin polymer. The dispersion can be mi~ed with polymer by high shear mixing, tumbling in a drum or directly metering through an extruder.
In any event, a homogeneous distribution of the stabilizer with the polymer is achieved without the danger of thermally degrading the polymer or additive and without agglomerating the stabilizer.
The advantage of having uniformly dispersed stabilizer is reflected in the aging characteristics of the finished product. When the additives are adequately dispersed, there are no localized areas starved of stabilizer which can fail due to polymer ogidation .
The amount of dispersion added to a thermoplastic resin will vary and depend, in part, upon the concentration of the dispersion, the actual thermoplastic resin and the effect desired. Usually, this is on the order of about 0.01 to about 2 percent by weight, preferably about 0.02 to about 1 percent by weight, based on the weight of the resin.
Whereas the exact scope of the instant invention is set forth in the appended claims, the following specific examples illustrate certain 2 ~ . 2 i ~
aspects of the present invention and more particularly, point out methods of evaluating the same. All parts and percentages are by weight unless otherwise specified. Particle size in microns, as reported herein, was determined using a MICROTRAC~
particle size analyzer.
~efinitions The following designations used in the E~amples and elsewhere herein have the following meaning:
Oxidative Induction Time (OLT) was determined at a temperature of 200C under an oxygen feed of 50 ml per minute. The test is a determination of o~idative degradation stability.
Average oxidative induction time is reported in minutes and described in chapter 9 of the following publication:
H. E. Bair Thermal Analysis of Additives in Polymers Thermal Characteri~ation of Polymer Materials E. A. Turi Ed.
Academic Press, 1981 New York ellowness Index (YI) was determined in accordance with ASTM D-1925-70, before and after aging at 80C for a certain time period. A Pacific Scientific Colorgard System/OS instrument was used in determination of the color.
2 ~ s~ ~i 2 SPAN 80: Sorbitan monooleate supplied by Imperial Chemical Industries Ltd.
SPAN 20: Sorbitan monolaurate supplied by Imperial Chemical In~dustries Ltd.
Ethanox~ 330:
(1,3,5-trimethyl)-2,9,6-tri(3,5-di-tert-butyl-4 hydro~ybenzyl)benzene, manufactured by Ethyl Corporation.
Irganox~ 1010:
~tetrakis [methylene-3(3',5'-di-tert-butyl-4' hydroxyphenyl)propionate~ methane, marketed by Ciba-Geigy Corporation.
PA-l: VCARSIL~ PA-l is a polyether silicone processing aid from Vnion Carbide Chemicals and Plastics Company Inc., Danbury, CT.
Vano~ 1001: ~ substituted aromatic amine sold by R. T. Vanderbilt Company, Inc. as a general purpose antioxidant.
Cynox 711: Ditridecylthiodiproprionate made by American Cyanamid Company.
Weston 399B: Tris(nonylphenyl)phosphite available from Borg-Warner Chemical Co.
1 ~I LLDPE: Copolymer of ethylene/l-butene having a melt index of 1 and density of 918 Kg/m3 2~9~ rj~
g - gram or grams.
Example 1 309 Ethanox~ 330 (50% by weight of the particles had a particle size less than 75.5 microns) 309 micronized Ethano~ 330 (50% by weight of the particles had a particle size less than 3.9 microns), and 60g SPAN 80 were blended in a Cowles mixer at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 4 hours of centrifugation at a force of 1400G's.
Example 2 40g micronized Irganox~ 1010 (50% by weight of the particles had a particle size less than about 3.2 microns) 60g of Span 80 were blended in a Cowles mixer at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 1 hour of centrifugation at a force of 1400G's.
Egample 3 40g micronized Irganox 1010 (50% by weight of the particles had a particle size less than about 3.2 microns) and 60g of Span 20 were blended in a Cowles mi~er at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 1 hour of centrifugation at a force of 1400G's.
E~m~
lg PA-l and lg Weston 399B were mixed. They were not mlsclle.
- 16 ~ 2, E~ample 5 E~ample 4 was repeated except that 2g of Span 20 was added. The solution was mi~ed and was miscible.
This Example demonstrates the improved miscibility of liquids when Span 20 was added to the formulation.
E~amPle 6 lg PA-l and lg SPAN 80 were mixed. They formed a miscible solution.
~ample 7 lg Weston 399B and lg SPAN 80 were mi~ed. They formed a miscible solution.
E~am~le 8 lg glyceryl trioleate and lg Weston 399B were mi~ed.
They formed a miscible solution.
E~ample 9 lg Cyanox 711, 19 Vanox 1001 and lg glyceryl trioleate were mixed~ They formed a miscible solution.
Example 10 lg Vanox 1001, lg mineral oil and lg glycerol trioleate were mixed. They formed a miscible solution.
Example 11 72g micronized Ethanox 330 (50% by weight of the particles had a particle size less than about 3.9 microns) and 60g glyceryl trioleate were blended in a Cowles mixer at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 4 hours of centrifugation at a force of 140OG's.
Example 12 40g PA-l and 90g SPAN 80 were mixed. They formed a miscible solution. To the above solution 40g micronized Ethanox 330 (50~ by weight of the particles had a particle size less than about 3.g microns) and 40g unground Ethanox 330 ~50% by weight of the particles had a particle size less than about 75.5 microns) were blended in a Cowles mixer at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 4 hours of centrifugation at a force of 1400G's.
~xample 13 Respective compositions, the formulations of which are described in Table 1 hereunder, were compounded in a Henschel mixer and extruded at 218C through a strand die fitted to a Brabender extruder and pelletized.
- 18 - 2~
Formulation Z YI lday 80~C YI 7day6 80-C OIT(min) 99.95% LLDPE
0.052 Micronized Irganox 10l0 20 20 28.2 99.85~ LLDPE 12 12 30.3 0.05% Micronized Irganox 1010 0.1% SPAN 80 (The Irganox l010 and SPAN 80 were added to the LLDPE a6 a di6per6ion.
Ihe di6per6ion6 was formed by blending the component6 together in a Cowle6 mixer at 1500 rpm for 5 minutes.) The above results demonstrate the improvement in the stabilization of the polymer when the dispersion of the invention was employed.
Petailed pe~ription of the Invention By the teachings of this present invention, stable dispersions of polymer stabilizers are provided using normally li~uid fatty acid esters of polyhydric organic compounds as the liquid or continuous phase of the dispersion. The stable dispersions of the invention can be distributed uniformly in various polymers, and with particular advantage in thermoplastics, by blending the dispersion and polymer by a variety of mixing techniques known in the art including melt extrusion.
The liquid or continuous phase of the dispersions of this invention comprises a normally liquid, at ambient conditions, fatty acid ester of a polyhydric organic compound. The fatty acids from which the esters are derivable can be saturated or ethylenically unsaturated and usually have from 12 to 18 carbon atoms. The preferred class of polyhydric compounds, in turn, from which the fatty acid esters are derivable consist of carbon, hydrogen and oxygen and contain from three to six hydroxyl groups which can be the terminal hydroxyl groups of etho~ylated moieties. Oxygen can also be present as the cyclic ether group, I
H-C~
¦ O, in which event the polyhydric H-C/
I
alcohol has no more than four hydroxyl groups.
Oxygen can also be present in the polyhydric alcohol as acyclic ether linkages such as in the --4-- 2 0 ~
aforementioned hydroxyl-terminated ethogylated or poly(o~yethylene) moieties. It is to be understood that the fatty acid ester can contain zero or from one to si~ hydro~yl-terminated poly(ogyethylene) chains. When the ester does contain such chains, i.e., -(OC2H4)n-OH, the total average number (n) Of o~yethylene units in the ester is a positive number, usually ranging from about 1 to about 100. The continuous phase of the dispersions of this invention may comprise any combination of the aforesaid types of fatty acid esters.
Most preferably the continuous phase of the dispersions contain fatty acid esters of sorbitan, glycerol or mixtures thereof. Illustrative of suitable sorbitan and glyceryl esters are sorbitan monooleate, sorbitan monolaurate, sorbitan trioleate, glyceryl trioleate, glyceryl monooleate, and the like. Various sorbitan esters, such as sorbitan monooleate and sorbitan monolaurate, are available commercially as Span 80 a~d Span 20 respectively from Imperial Chemical Industries Ltd. (ICl). Similarly, various glyceryl esters are commercially available from Witco Corporation. Poly(o~yethylene)-containing or ethoxylated derivatives of the sorbitan or glyceryl esters can also be used in the present invention. The latter materials are also commercially available from ICI, such as for e~ample, Tween 20. Of the above ester compositions, especially preferred as the continuous phase of the dispersions of this invention are sorbitan monooleate, sorbitan monolaurate and glyceryl trioleate.
2~9~ ~i2 The continuous phase of the dispersion may also contain other liquids which are miscible in the fatty acid esters of the polyhydric organic compound. Preferably, the second liqui~ of the continuous phase also improves the properties of the polymer. Illustrative liquids include, but are not limited to, processing aids, liquid stabilizers and lubricants. Liquid stabilizers include organomodified silicones such as hindered amine silicones, including W SIL~ 299 (Enichem Co.).
Especially preferred organomodified silicones are polyether silicone processing aids such as VCARSIL~
PA-l (Union Carbide Chemicals and Plastics Company Inc.) The above-described fatty acid esters of polyhydric coumpounds are known to be useful as lubricants and surface active agents. Therefore, their use as the continuous phase of the dispersions of this invention allows for the elimination or reduction in the concentration of other additives for such purposes.
Improved performance of a polymer is noted as the stabilizers become more uniformly distributed within the polymer becomes more uniform. In particular, color and resistance to thermal degradation improve as stabilizers, such as antio~idants are more uniformly dispersed within the polymer. Illustrative of but not limited to then types of stabilizers which can be used in the present invention are ultraviolet light stabilizers, thermostabilizers, antioxidants, catalyst deactivators and acid neutralizers. Stabilizers are D-16~99 important additives because of their ability to modify overall polymer performance. Because of their high cost relative to the cost of most polymers, it is essential that staoilizers are uniformly distributed throughout the polymer to realize ma~imum benefit.
As used herein, the term "stabilizer" is meant to include all materials which can be added to polymer compositions for the purpose of improving or retaining the polymer's properties under various conditions of exposure and use. Although many stabilizers are solids, liquid stabilizers can also be employed in the present invention. The better the dispersion of the stabilizer in the polymer, the better the stabilizer efficiency. Stabilizers contain polar moieties and often are particularly troublesome to disperse into relatively non-polar polymer resins, particularly polyolefin resins. For e~ample, the use of ETHANOX~ 330, a relatively high molecular weight and high melting (244C) antioxidant, in polypropylene and nylon theoretically offers high performance, but has been excluded from many applications because of the difficulty in obtaining uniform additive-resin dispersions. For similar reasons, relatively polar zinc oxide, a low-cost acid scavenger, also is not used routinely for stabilizing polyolefins because it is difficult to disperse uniformly. ~ore particularly, the present invention provides a solution to the problems associated with attempts to disperse polar additives into non-polar polymers.
Specific e~amples of the stabilizers component of the dispersions of this invention D~16899 - 7 - 2~3~ J
include: fatty amine, fatty amide antistatic agents and catalyst deactivators such as KEMAMINE~ and XEMAMIDE~ and ATMER~ 163 (witco Chemical Co.);
stabilizers including organic phosphites, and other organic phosphorus compounds, such as tri-n-dodecylphosphite, the bis-substituted pentaerythritol diphosphites such as bis~2,4-di-t-butylphenyl) pentaerythritol diphosphite, tris(mono-and di-nonylphenyl)phosphite IRGAFOS~ 168 (Ciba -Geigy); phosphonites including fluorophosphonites such as ETHANOX~ 398 (Ethyl Corp) and SANDOSTAB~
P-EPQ ~Sandoz); hindered phenols, such as octadecyl 3-(3',5'-di-t-butyl-4-hydro~yphenyl)- propionate, IONOL~ (Shell), TOPANOL~CA (ICI); IRGANOX~
antio~idants such as IRGANOX~ 1076, 1093, 1098 and IRGANOX~ 1010 (tetrakis[methylene-3(3'-5'-di-tert-butyl-4'hydro~yphenyl)propionate] methane) (Ciba-Geigy); and the ETHANOX~ antio~idants such as ETHANOX~ 330 (1,3,5-tri-methyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) benzene) and ETHANOX~ 702 (Ethyl Corp.); and ISONOX~ 129 (2,2'-ethylidene-bis(4,6-di-t-butyl)phenol) (Schenectady Chemical); the CYANOX~ antioxidants including CYANOX~ 1790 (American Cyanamid); the GOOD-RITE~ antioxidants including GOODRITE~ 3114 (B.F. Goodrich Chemical Co.); antio~idants/metal deactivators, such as the NAUGARD9 products such as NAUGARD~ XLl (Uniroyal Inc.) and IRGANOX~ MD 1024 (Ciba-Geigy); thiodipropionate stabilizers such as dilauryl thiodipropionate; hindered amine compounds such as those containing tetra alkyl-piperidinyl functionality, including the light stabilizers and W
- ~ - 2~3~v~
absorbers such as TIN W IN~ 149, TIN WIN~ 326 and 327, TIN W IN~ P, TIN W IN~ 622LD (Ciba-Geigy), CYANOX~ 3346 (American Cyanamid), GOO~RITE~ 304~ (B.F. Goodrich Chemical Co.); benzophenone stabilizers, such as CYASORB~- W 2098 (American Cyanamid), W INUL~M 90 and W INUL~ 490 (BASF); blends of organic phosphorus compounds and hindered phenol antioxidants including IRGANOX~ 1411, 1412, 501W, 712FF, B-225, B-215, and 900 (Ciba-Geigy); nucleating agents such as dibenzilydene sorbitol; acid neutralizers including metal o~ides such as zinc oxide; hydrotalcites; metal stearates; calcium lactate and the like.
The concentration of the dispersion, i.e., the weight of the discrete phase (stabilizer) in the liquid phase, is usually about 0.1 to about 80 percent by weight, generally about 1 to about 60 percent by weight and usually about 10 to about 50 percent by weight.
The dispersions of this invention are prepared by admixing the stabilizer with the normally liquid fatty ester of a polyhydric organic compound by using a high shear mi~er such as a COWLES~ mi~er.
Also within the scope of this invention are mi~tures of solid and liquid stabilizers as the discrete phase of the dispersion.
The process of the present invention can be used for dispersing the various polymer stabilizers in a wide variety of thermoplastic systems. The process can be advantageously employed with homopolymers, copolymers and polymer blends.
Illustrative of, but not limited to the polymers include polyolefins, such as high density 2 ~ r,; ~j ~
polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene, polyesters, polyvinyl chloride, polyacrylates, polystyrene, styrene-butadiene copolymers, polyvinyl chloride/polyvinylacetate copolymers, ethylene/
acrylic acid copolymers, ethylene/acrylic acid/vinyl acetate terpolymers and the like.
Stabilizers which are used to formulate the dispersions of this invention generally have the following particle size distribution: at least about 95% by weight of the particles have a diameter of less than 150 microns and about 20 percent by weight have a particle size of less than about 20 microns.
Preferably at least about 95~ by weight of the particles have a diameter of less than 100 microns and at least 35% by weight have a particle size of less than 10 microns. Even more preferable are stabilizers having an average particle size of less than 20 microns and more than 50% by weight less than 10 microns.
Particularly desirable for purposes of this invention are stabilizers having the particle size described above which are comprised of a bimodal size distribution. A bimodal distribution has two separate peaks around which the particles are clustered. Especially advantageous are those bimodal distributions where the weight fraction of the larger particles, relative to the smaller particles, is from about 30 to about 90 percent of the total weight of the particles and the ratio of the average particle size of the larger particle size is at least two and preferably from about 2 to about 100. The _ lo - 2~ 3~
dispersions having this particle size and weight distributions have been found to be not only e~tremely stable but also have a lower viscosity compared to dispersions only containing smal~er particles.
While not wishing to be bound by any specific theory, it is believed that the stability of the dispersions of this invention is due to the occurrence of controlled agglomeration. Controlled agglomeration is believed to result in a structure which extends through the whole li~uid volume and supports the individual particles, preventing the particles from settling. Consequently, there is no need to incorporate e~traneous ingredients in the dispersion, such as surfactants and the like, whose sole purpose is to ensure the stability of the dispersion.
As used throughout this specification, which includes the claims, ~stable dispersions" are those wherein there is less than about 5 percent by volume separation of the liguid phase, evidenced by the formation of a two-phase system, after centrifugation of the dispersions under a force of one-hundred times the force of gravity (lOOG) for one hour.
Particularly desirable are those dispersions which exhibit less than about 5 percent by volume separation after centrifugation under a force of 1400G for 9 hours. Dispersions which exhibit less than about 5 percent by volume separation after centrifugation under a force of 1400G for 4 hours are considered as stable, under ambient conditions, for at least 6 months. As used herein the phrase dispersion also encompasses suspensions and emulsions.
2 ~ J
The dispersion containing the desired stabilizer in dispersed form is added directly to the thermoplastic resin which can be in either the form of solid particles (in pellet, granule, powder, etc., form) or in the molten state. In other words, the stable dispersions of the present invention can be pre-blended with polymer particles before polymer processing operations such as melt e~trusion, injection molding and the like, or the dispersion can be added directly to a molten polymer during its processing. The compounding of the dispersion and thermoplastic resin may be done by spraying or by mixing or tumbling the resin and suspension in a ribbon blender, utilizing a two-roll mill, an e~truder, including single screw and multiple screw e~truders, a Banbury (Farrel Corp.) or Brabender mixer. Suitable procedures and equipment will readily occur to those skilled in the art of polymer processing. Concentrates or master batches of the dispersion and resin may be produced and blended with virgin resin such as on a mill before final processing. The rolls on a two-roll mill may operate at different speeds and temperatures. In spite of the simplicity of the milling operation, extrusion is usually preferred for blending the suspension and resin since an e~truder can operate continuously, for example to produce strands that may be cut by a rotating knife to produce pellets.
The stable dispersion can be added to the synthetic resin at the end of the resin manufacturing process, such as directly after resin polymerization or polycondensation, for example while it is still ~ ~3 ~ 2 t~
molten or to powdered or pelleted polymer particles.
However, it also is possible, and often more convenient, to admix the dispersion with the synthetic resin subsequently during one of its myriad processing stages, for e~ample prior to or during extrusion. Using a fluid dispersion not only facilitates the mixing/dispersing of the additive with the polymer, but also makes it easier to control the amount of stabilizer mixed with the resin polymer. The dispersion can be mi~ed with polymer by high shear mixing, tumbling in a drum or directly metering through an extruder.
In any event, a homogeneous distribution of the stabilizer with the polymer is achieved without the danger of thermally degrading the polymer or additive and without agglomerating the stabilizer.
The advantage of having uniformly dispersed stabilizer is reflected in the aging characteristics of the finished product. When the additives are adequately dispersed, there are no localized areas starved of stabilizer which can fail due to polymer ogidation .
The amount of dispersion added to a thermoplastic resin will vary and depend, in part, upon the concentration of the dispersion, the actual thermoplastic resin and the effect desired. Usually, this is on the order of about 0.01 to about 2 percent by weight, preferably about 0.02 to about 1 percent by weight, based on the weight of the resin.
Whereas the exact scope of the instant invention is set forth in the appended claims, the following specific examples illustrate certain 2 ~ . 2 i ~
aspects of the present invention and more particularly, point out methods of evaluating the same. All parts and percentages are by weight unless otherwise specified. Particle size in microns, as reported herein, was determined using a MICROTRAC~
particle size analyzer.
~efinitions The following designations used in the E~amples and elsewhere herein have the following meaning:
Oxidative Induction Time (OLT) was determined at a temperature of 200C under an oxygen feed of 50 ml per minute. The test is a determination of o~idative degradation stability.
Average oxidative induction time is reported in minutes and described in chapter 9 of the following publication:
H. E. Bair Thermal Analysis of Additives in Polymers Thermal Characteri~ation of Polymer Materials E. A. Turi Ed.
Academic Press, 1981 New York ellowness Index (YI) was determined in accordance with ASTM D-1925-70, before and after aging at 80C for a certain time period. A Pacific Scientific Colorgard System/OS instrument was used in determination of the color.
2 ~ s~ ~i 2 SPAN 80: Sorbitan monooleate supplied by Imperial Chemical Industries Ltd.
SPAN 20: Sorbitan monolaurate supplied by Imperial Chemical In~dustries Ltd.
Ethanox~ 330:
(1,3,5-trimethyl)-2,9,6-tri(3,5-di-tert-butyl-4 hydro~ybenzyl)benzene, manufactured by Ethyl Corporation.
Irganox~ 1010:
~tetrakis [methylene-3(3',5'-di-tert-butyl-4' hydroxyphenyl)propionate~ methane, marketed by Ciba-Geigy Corporation.
PA-l: VCARSIL~ PA-l is a polyether silicone processing aid from Vnion Carbide Chemicals and Plastics Company Inc., Danbury, CT.
Vano~ 1001: ~ substituted aromatic amine sold by R. T. Vanderbilt Company, Inc. as a general purpose antioxidant.
Cynox 711: Ditridecylthiodiproprionate made by American Cyanamid Company.
Weston 399B: Tris(nonylphenyl)phosphite available from Borg-Warner Chemical Co.
1 ~I LLDPE: Copolymer of ethylene/l-butene having a melt index of 1 and density of 918 Kg/m3 2~9~ rj~
g - gram or grams.
Example 1 309 Ethanox~ 330 (50% by weight of the particles had a particle size less than 75.5 microns) 309 micronized Ethano~ 330 (50% by weight of the particles had a particle size less than 3.9 microns), and 60g SPAN 80 were blended in a Cowles mixer at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 4 hours of centrifugation at a force of 1400G's.
Example 2 40g micronized Irganox~ 1010 (50% by weight of the particles had a particle size less than about 3.2 microns) 60g of Span 80 were blended in a Cowles mixer at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 1 hour of centrifugation at a force of 1400G's.
Egample 3 40g micronized Irganox 1010 (50% by weight of the particles had a particle size less than about 3.2 microns) and 60g of Span 20 were blended in a Cowles mi~er at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 1 hour of centrifugation at a force of 1400G's.
E~m~
lg PA-l and lg Weston 399B were mixed. They were not mlsclle.
- 16 ~ 2, E~ample 5 E~ample 4 was repeated except that 2g of Span 20 was added. The solution was mi~ed and was miscible.
This Example demonstrates the improved miscibility of liquids when Span 20 was added to the formulation.
E~amPle 6 lg PA-l and lg SPAN 80 were mixed. They formed a miscible solution.
~ample 7 lg Weston 399B and lg SPAN 80 were mi~ed. They formed a miscible solution.
E~am~le 8 lg glyceryl trioleate and lg Weston 399B were mi~ed.
They formed a miscible solution.
E~ample 9 lg Cyanox 711, 19 Vanox 1001 and lg glyceryl trioleate were mixed~ They formed a miscible solution.
Example 10 lg Vanox 1001, lg mineral oil and lg glycerol trioleate were mixed. They formed a miscible solution.
Example 11 72g micronized Ethanox 330 (50% by weight of the particles had a particle size less than about 3.9 microns) and 60g glyceryl trioleate were blended in a Cowles mixer at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 4 hours of centrifugation at a force of 140OG's.
Example 12 40g PA-l and 90g SPAN 80 were mixed. They formed a miscible solution. To the above solution 40g micronized Ethanox 330 (50~ by weight of the particles had a particle size less than about 3.g microns) and 40g unground Ethanox 330 ~50% by weight of the particles had a particle size less than about 75.5 microns) were blended in a Cowles mixer at 1500 RPM for 5 minutes. The resulting dispersion was sufficiently stable to withstand 4 hours of centrifugation at a force of 1400G's.
~xample 13 Respective compositions, the formulations of which are described in Table 1 hereunder, were compounded in a Henschel mixer and extruded at 218C through a strand die fitted to a Brabender extruder and pelletized.
- 18 - 2~
Formulation Z YI lday 80~C YI 7day6 80-C OIT(min) 99.95% LLDPE
0.052 Micronized Irganox 10l0 20 20 28.2 99.85~ LLDPE 12 12 30.3 0.05% Micronized Irganox 1010 0.1% SPAN 80 (The Irganox l010 and SPAN 80 were added to the LLDPE a6 a di6per6ion.
Ihe di6per6ion6 was formed by blending the component6 together in a Cowle6 mixer at 1500 rpm for 5 minutes.) The above results demonstrate the improvement in the stabilization of the polymer when the dispersion of the invention was employed.
Claims (16)
1. A stable dispersion wherein the discrete phase comprises a polymer stabilizer and the continuous phase comprises a normally liquid fatty acid ester of a polyhydric organic compound or mixture.
2. A stable dispersion as defined in claim 1 wherein the polymer stabilizer comprises solid particles, at least about 95% by weight of the solid particles having a particle size of less than 150 microns and at least 20% by weight of said particles having a particle size of less than 20 microns.
3. A stable dispersion as defined in claim 1 wherein the polymer stabilizer comprises solid particles, the particle size of which has a bimodal distribution, the ratio of the large average size diameter particles to the small average particle size diameter being at least about 2.
4. A stable dispersion as defined in claim 1 wherein the continuous phase comprises a fatty acid ester of a polyhydric alcohol having from three to six hydroxyl groups.
5. A stable dispersion as defined in claim 1 wherein the continuous phase comprises sorbitan monooleate, sorbitan monolaurate, glyceryl trioleate or mixtures thereof.
6. A stable dispersion as defined in claim 1 wherein the continuous phase comprises a normally liquid fatty ester of a polyhydric organic compound and an organomodified silicone.
7. A stable dispersion as defined in claim 1 wherein the continuous phase comprises a normally liquid fatty acid ester of a polyhydric organic compound and a polyether silicone.
8. A method for combining a polymer stabilizer and a polymer which method comprises providing to the polymer a stable dispersion wherein the discrete phase comprises a polymer stabilizer and the continuous phase comprises a normally liquid fatty acid ester of a polyhydric organic compound.
9. The method of claim 8 wherein the discrete phase comprises solid particles having at least about 95% by weight solid particles having a particle size of less than 150 microns and at least 20% by weight of said particles having a particle size of less than 20 microns.
10. The method of claim 8 wherein the stable dispersion is added to the polymer while the polymer is in the form of a solid particle.
11. The method of claim 8 wherein the stable dispersion is added to the polymer while the polymer is in a molten state.
12. The method of claim 8 wherein the sorbitan or glyceryl ester is sorbitan monooleate, sorbitan monolaurate,sorbitan trioleate, glyceryl monooleate and mixtures thereof.
13. The method of claim 8 wherein the continuous phase comprises a normally liquid fatty acid ester of a polyhydric compound and an organomodified silicone.
14. The method of claim 8 wherein the continuous phase comprises a normally liquid fatty acid ester of a polyhydric organic compound and a polyether silicone.
15. The method of claim 8 wherein the polymer stabilizer and the polymer are combined by high shear mixing.
16. The method of claim 8 wherein the polymer stabilizer and the polymer are combined by melt extrusion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86114092A | 1992-03-31 | 1992-03-31 | |
| US7/861,140 | 1992-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2092952A1 true CA2092952A1 (en) | 1993-10-01 |
Family
ID=25334994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2092952 Abandoned CA2092952A1 (en) | 1992-03-31 | 1993-03-30 | Dispersions of polymer additives in fatty acid esters |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0563906A1 (en) |
| JP (1) | JPH0641348A (en) |
| AU (1) | AU652689B2 (en) |
| BR (1) | BR9301365A (en) |
| CA (1) | CA2092952A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4339984A1 (en) * | 1993-11-24 | 1995-06-01 | Rhein Chemie Rheinau Gmbh | Rubber chemicals preparation |
| JP5020445B2 (en) * | 2001-07-23 | 2012-09-05 | 中部電力株式会社 | Recycled vinyl chloride resin composition |
| WO2004048312A1 (en) * | 2002-11-26 | 2004-06-10 | Ciba Specialty Chemicals Holding Inc. | Phenolic antioxidants in crystalline form |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932634A (en) * | 1973-06-28 | 1976-01-13 | Pfizer Inc. | High potency vitamin water dispersible formulations |
| EP0200684B1 (en) * | 1985-05-02 | 1990-08-01 | Ciba-Geigy Ag | Method for stabilizing spherical polymerized polyolefins |
| US5204022A (en) * | 1989-08-11 | 1993-04-20 | Eastman Kodak Company | Solid-form additive systems dispersible in aqueous media |
| GB9008847D0 (en) * | 1990-04-19 | 1990-06-13 | Metacol Limited | The incorporation of additives into polyesters |
| JPH05247259A (en) * | 1992-01-18 | 1993-09-24 | Hoechst Ag | Thermoplastic molding composition |
-
1993
- 1993-03-30 BR BR9301365A patent/BR9301365A/en not_active Application Discontinuation
- 1993-03-30 AU AU35578/93A patent/AU652689B2/en not_active Ceased
- 1993-03-30 JP JP9394593A patent/JPH0641348A/en not_active Withdrawn
- 1993-03-30 EP EP93105292A patent/EP0563906A1/en not_active Withdrawn
- 1993-03-30 CA CA 2092952 patent/CA2092952A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0641348A (en) | 1994-02-15 |
| BR9301365A (en) | 1993-10-13 |
| EP0563906A1 (en) | 1993-10-06 |
| AU652689B2 (en) | 1994-09-01 |
| AU3557893A (en) | 1993-10-07 |
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