WO1999035184A1 - Composition polymere - Google Patents

Composition polymere Download PDF

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Publication number
WO1999035184A1
WO1999035184A1 PCT/NL1998/000463 NL9800463W WO9935184A1 WO 1999035184 A1 WO1999035184 A1 WO 1999035184A1 NL 9800463 W NL9800463 W NL 9800463W WO 9935184 A1 WO9935184 A1 WO 9935184A1
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WO
WIPO (PCT)
Prior art keywords
polymer composition
composition according
solid substance
polymers
particles
Prior art date
Application number
PCT/NL1998/000463
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English (en)
Inventor
John Wilhelm Geus
Original Assignee
Universiteit Utrecht
U-Cat B.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from NL1007985A external-priority patent/NL1007985C2/nl
Application filed by Universiteit Utrecht, U-Cat B.V. filed Critical Universiteit Utrecht
Priority to AU87532/98A priority Critical patent/AU8753298A/en
Publication of WO1999035184A1 publication Critical patent/WO1999035184A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/262—Alkali metal carbonates

Definitions

  • This invention relates to the use of finely divided, solid, inorganic compounds of basic reaction, in polymers containing components of acid reaction, such as halogens. More particularly, this invention relates to the stabilization of polymers or synthetic resins against discoloring by the presence of such acid components, and against the occurrence of corrosion thereby caused, respectively. In addition, _ this invention relates to sheetlike inorganic materials serving as supports for polymerization catalysts.
  • Polymers in which the problems of corrosion and/or discoloring occur are inter alia polymers prepared by catalytic polymerization using Ziegler-Natta catalysts.
  • Such catalysts usually consist of a chloride of titanium or vanadium, which is treated with an aluminum alkyl. It is technically cumbersome to remove these catalysts completely, or substantially completely, from the polymers. Hydrolysis of the chlorides leads to the formation of hydrogen chloride. In the processing of the polymers, hydrogen chloride is released from the polymer, which leads to corrosion of the processing equipment .
  • polymers based on vinyl chloride are formed by the polymers based on vinyl chloride. In these polymers, too, (for instance through reaction with water) , hydrogen chloride may be released.
  • the invention also covers polymers prepared with acid catalysts, such as polymers or synthetic resins prepared from epichlorohydrin, as well as polymers prepared using Friedel- Crafts catalysts.
  • a last group is formed by polymers manufactured through suspension polymerization, such as polymers based on styrene, such as polystyrene, styrene-acrylonitrile polymers and acrylonitrile-butadiene-styrene (ABS) polymers.
  • alkaline catalysts such as calcium phosphate, magnesium hydroxide or calcium carbonate. These catalysts are removed from the polymer by a treatment with sulfuric acid or hydrochloric acid. Generally, a slight amount of acid then remains behind in the polymer.
  • the use of polymers has increased enormously. In prolonged use of the polymers, the durability of polymers appears to be an increasingly important factor. Accordingly, there is a great need for compounds and methods for stabilizing such polymers.
  • the mineral hydrotalcite is a mixed magnesium-aluminum hydroxide/carbonate of the general formula
  • hydrotalcites Mg ⁇ -. X A1 X (OH) 2 + ⁇ .mH 2 0.
  • the compounds considered to fall under the hydrotalcites have a structure, the hydrotalcite structure, built up from layers of metal ions with hydroxyl groups on both sides; the layers are mutually bonded by hydrogen bridges.
  • trivalent ions for bivalent ions, there is a positive charge of the layers, which is compensated by incorporation of anions between the hydroxyl groups of the layers.
  • carbonate ions are incorporated.
  • other anions can also be properly included in a hydrotalcite structure.
  • Compounds having a hydrotalcite structure comprise a series of bivalent and trivalent metal ions.
  • hydrotalcites The preparation of hydrotalcites is discussed in US-A 3,539,306 and in GB-A 1 348 702. In the latter publication, the preparation of a whole series of hydrotalcites with different metal ions is described. The preparation of hydrotalcites with two different bivalent metal ions is mentioned in DE-C 2061 114.
  • the surface of solid particles of basic reaction will generally react faster with halogen hydrogen than the interior of the solid particles. In view of this, it seems attractive to use solid particles that are as small as possible. In a conglomerate of small solid particles, however, pores of the same dimensions as the particles occur. Because the surfaces of virtually all substances of alkaline reaction are hydrophilic, water will condense in the pores and on the surface upon exposure to atmospheric air. ater- covered inorganic solid particles exhibit a slight interaction with polymers, which are generally hydrophobic. As a result, it is not quite possible to properly disperse the inorganic solid particles in the polymer; the small elementary inorganic particles will adhere more strongly to each other than to the polymer. Further, the water that is present in the conglomerate of small solid particles will evaporate upon a thermal treatment. This gives rise to bubbles in the polymer when shaping the polymer.
  • the elementary particles occur as porous conglomerates; obviously, the dimensions of these conglomerates are of great importance for the dispersibility.
  • the patent refers to second-order particle sizes. The patent mentions that these conglomerates may not be greater than 5 ⁇ m.
  • hydrotalcites with two different bivalent metal ions. At least one of the metal ions is selected from Mg, Ca, Sr, and Ba, and at least one from the group of Zn, Cd, Pb, and Sn. At present, however, because of the health risks and the danger of environmental pollution, incorporating Cd and Pb compounds in particular, into polymers is considered undesirable.
  • the trivalent metal ion in the hydrotalcite structure is preferably aluminum.
  • requirements are imposed on the dimensions of the elementary particles and on the (porous) conglomerates of the elementary particles.
  • the BET surface area should not be more than 30 m 2 per gram and the size of the conglomerates is not more than about 5 ⁇ m, preferably not more than 2 ⁇ m and more preferably not more than 1 ⁇ m.
  • EP-B 0 189 899 gives a very extensive list of additives that lead to a higher stability against discoloring and increase stability at higher temperatures. Mentioned, among others, are beta-diketones .
  • polyvinyl chloride polymers are discussed, to which, for the purpose of stabilization, a hydrotalcite, magnesium oxide and a beta-diketone or a zinc salt of an organic acid has been added.
  • the BET surface area of the hydrotalcite is less than about 50 m 2 per gram and in particular less than 20 m 2 per gram.
  • the dimensions of the porous conglomerates are less than 5 ⁇ m and preferably less than 1 ⁇ m.
  • the magnesium oxide is added to bind the water and the carbon dioxide that is released upon reaction of acid compounds with the hydrotalcite. The binding of water and carbon dioxide prevents the formation of bubbles in the polymer.
  • EP-B 0 301 509 mentions the use of dispersed hydrotalcites for preventing adherence of polymer foils.
  • the hydrotalcite must be present as porous conglomerates which approximate the spherical shape as closely as possible.
  • the size of these conglomerates is 1 to 8 ⁇ m, preferably 2 to 6 ⁇ m, and more preferably 3 to 6 ⁇ m.
  • EP-A 0 052 331 relates to dispersing a mixed hydroxide of magnesium and aluminum in polymers to avoid discoloring and corrosion in the processing.
  • the BET surface area of the hydroxide should not be greater than 40 m 2 per gram and the mean size of the conglomerates should not exceed about 5 ⁇ m.
  • hydrotalcites generally consist of smaller elementary particles, a hydrothermal treatment is employed. This increases the size of the elementary particles without loss of the structure through desorption of structurally bound water.
  • such a hydrothermal treatment is costly.
  • an alkali metal salt of a fatty acid is provided to improve the interaction with the polymer.
  • a long series of conventional additives are mentioned, which can be added to the inorganic powder, such as beta-diketones .
  • the invention is based on the surprising insight that an excellent stabilization of polymers against discoloring and against the release of corrosive acid compounds can be achieved by homogeneous dispersion in the polymer of an inorganic, solid substance of alkaline reaction, consisting of elementary particles which are mutually not bonded or weakly bonded. These particles should possess a size of less than 0.5 ⁇ m.
  • the invention accordingly relates to a stabilized polymer composition
  • a stabilized polymer composition comprising at least one thermoplastic polymer having homogeneously dispersed therein elementary particles of an inorganic solid substance of alkaline reaction, of a particle size of not more than 0.5 ⁇ m.
  • the solid substance consists of elementary particles of a size (diameter) of less than 0.5 ⁇ m, preferably less than 0.2 ⁇ m, and more preferably less than 0.1 ⁇ m.
  • 'homogeneous' is understood to mean that the number of inorganic particles per mm 3 in the polymer differs by not more than a factor of three, and preferably by not more than a factor of two.
  • the elementary particles should not be agglomerated to such an extent that units greater than 0.5 ⁇ m are formed. In the case where the particles do exhibit some agglomeration, the cohesive forces should be so slight that during dispersal in the polymer a break-up of the agglomerate occurs.
  • the amount of solid particles of alkaline reaction which is preferably included in the polymer varies within wide limits. This amount is especially determined by the extent of stabilization that is desired and the amounts, of acid components that may be released. In general, this amount will vary from 0.05 to 10% by weight, based on the weight of the polymer.
  • the polymer In a number of polymers, it may be of importance that the polymer is transparent. When admixing solid substances, this should be taken into account. If particles are used whose dimensions are less than the wavelength of the light, little scatter of the light occurs, so that transparency remains high. In that connection, it may therefore be useful to use sheetlike particles of a thickness less than the wavelength of the light, while the lateral dimensions can be greater.
  • various types of polymers and polymer mixtures can be used in the polymer composition. Contemplated in view of the objective of the invention are especially polymers and polymer mixtures in which components can be formed which, owing to their acid character, can give rise to discoloring and/or corrosion.
  • Examples include the types of polymer mentioned in the introduction, of which especially the vinyl chloride polymers, styrene polymers and the Ziegler-Natta polymers (polyethylene, polypropylene and variations thereof) are commercially important.
  • alkaline metal oxides, carbonates, hydroxides or hydrotalcites can be used. It is surprising that with such small particles, whose BET surface area can be greater than 50 m 2 per gram, good results can be achieved, while the present state of the art indicates that the dimensions of the particles must not be selected to be too small.
  • hydrotalcites or hydroxides (which may or may not be of two different metal ions) are used with a BET surface area of less than 30 m 2 per gram.
  • the inorganic powders according to our invention by contrast, have greater BET surface areas.
  • the good action of inorganic powders for the -invention can be attributed to the fact that the elementary particles are not bound to each other and therefore do not include narrow pores. As a result, capillary condensation of water does not occur. Because the elementary particles are not intimately bonded to each other, it is very well possible to properly disperse the particles in the polymer.
  • a first eligible method for this purpose is the so-called flame hydrolysis.
  • a suitable volatile chloride is introduced into a hydrogen-oxygen flame, whereby the chloride reacts with water.
  • a suitable example is aluminum chloride, which reacts according to
  • the extremely finely divided aluminum oxide formed is separated with an electrostatic precipitator .
  • an electrostatic precipitator With the inorganic powders according to the invention, it is of importance to prevent condensation of water vapor on the powder. This can be done by operating the precipitator at elevated temperature and cooling it after ending the production in an anhydrous gas stream.
  • Another method for preparing finely divided inorganic powders according to the invention proceeds via so-called aerogels.
  • the precipitation of the desired compound is carried out such that eventually a suspension of the compound in a non-aqueous liquid, such as ethyl alcohol, is obtained.
  • a non-aqueous liquid such as ethyl alcohol
  • This can be done by performing the precipitation in alcohol, for instance by hydrolysis with the stoichiometric amount of water of an alcoholate of the desired metal. It is also possible to perform the precipitation in aqueous medium and then to replace the water with alcohol. Under pressure, the suspension is now heated to a temperature above the critical point of the liquid, whereafter the supercritical phase is allowed to escape from the autoclave.
  • the solid particles are not pressed onto each other, so that mutually isolate particles are obtained.
  • water cannot be used, because under the hydrothermal conditions emerging upon heating of water to the critical temperature, the small solid particles will generally react to form (very) large crystals.
  • the very thin structure of the material is rapidly lost. Exposure to water vapor must therefore be avoided, or a suitable compound must be priorly adsorbed onto the surface.
  • oxalates Another method for the preparation of inorganic powders starts from oxalates.
  • metal oxalates At elevated temperature, metal oxalates first lose water of crystallization, whereupon decomposition into oxides or metals occurs. With base metals, such as magnesium or zinc, decomposition proceeds to oxides, whereby carbon monoxide is formed. In more noble metals, such as nickel or copper, the metal and carbon dioxide are formed. In the latter case, the decomposition will have to be performed in a stream of an oxygen-containing gas, to prepare the desired oxides.
  • the oxalates decompose into extremely small particles, which exhibit a large BET surface area. The elementary particles, however, will exhibit some coherence.
  • the conglomerates can be easily disintegrated by mechanical operations, such as grinding.
  • oxalates of the desired metals, or an aqueous suspension of the oxalates are charged to a fluidized bed of wear-resistant particles, which is maintained at a temperature above the decomposition temperature of the oxalate.
  • Oxalate particles or oxide particles initially deposited on the wear-resistant particles will, owing to wear and by the gas stream, be transported out of the fluidized bed as extremely small particles.
  • the particles are separated with a cyclone and/or an electrostatic precipitator.
  • finely divided hydrotalcites of a water content of less than 2% by weight are used.
  • the water content of the hydrotalcite is calculated from the value of n.
  • the hydrotalcite particles can be prepared by precipitating hydrotalcites by mixing a solution of a carbonate of an alkali metal with a solution of nitrates or chlorides of the bivalent and trivalent ions of which it is desired to prepare the hydrotalcite.
  • a carbonate of an alkali metal Preferably, sodium carbonate is used as carbonate of an alkali metal, and magnesium nitrate and aluminum nitrate as bivalent and trivalent ions.
  • An advantage of this combination is that such a hydrotalcite does not contain any heavy metal ions. After filtering off and thorough washing out, the hydrotalcites are dried at a temperature between 180 and 220°C. Surprisingly, it has been found that very thorough washing-out of the precipitate leads to a considerable improvement of the dispersibility of the hydrotalcite.
  • a characteristic property of properly washed-out materials is that they exhibit only a small number of peaks in the X-ray diffraction pattern.
  • the above-described material washed out three times, exhibits, for instance, only nine peaks, viz. at the d-values: 7.577, 3.792, 2.592, 2.573, 2.550, 2.524, 2.313, 1.521 and 1.492.
  • inorganic materials consisting of very thin sheets have the property that admixture does not impair the transparency of plastics and hence the ability to provide the plastics with brilliant colors.
  • hydrotalcites in the form of thin sheets, the lateral dimensions of the sheets being much greater than the thickness of the sheets.
  • sheetlike hydrotalcites are used whose BET surface area is of the same order of magnitude as that of the above-mentioned conventionally prepared hydrotalcites, viz. about 70 m 2 per gram.
  • the elementary particles of the hydrotalcites are thin sheets of a thickness of less than 5 nm and lateral dimensions of 0.1 to 3 ⁇ m.
  • Such sheetlike hydrotalcites are characterized by the so-called t-plot, which can be calculated from the physical adsorption of nitrogen.
  • clay minerals in polymers. This is primarily done to reduce the permeability of the polymer to molecules such as water. In addition, uniformly admixed clay minerals can increase the mechanical strength of the polymer composition. So far, clay minerals have not been mentioned for the neutralization of hydrogen chloride.
  • the provision of fillers for improving the above two properties, permeability and mechanical strength, is an additional objective of the present invention, in addition to the objective of incorporating hydrogen chloride released. It is known to expand the intermediate layer of natural clay minerals by reaction with quaternary ammonium ions with long hydrocarbon groups or with inorganic colloidal groups. Such materials are described in EP-A 0 747 322 and in WO-A 97/31057.
  • synthetic clay minerals are used, prepared by reaction of bivalent metal ions with silicon dioxide at a pH of 5 to 9.
  • the preparation of such clay minerals is described in detail in WO-A 9607613.
  • the stacking of the elementary clay sheets in such synthetic clay minerals can be eminently controlled.
  • the preparation of the clay minerals is carried out such that the elementary clay sheets are hardly stacked, if at all, and assume a so-called house-of-cards structure. If acid groups are desired on the surface of the clay sheets, the precipitation can be performed using urea or by addition of ammonium hydroxide.
  • ammonium ions neutralize the excess of negative charge on the clay sheets.
  • the NH 4 + ions decompose to form NH 3 , while protons remain behind on the surface.
  • the number of acid groups on the surface of the elementary clay sheets is relatively small.
  • the metal ions present in the octahedron layer react with the acid, so that neutralization occurs.
  • the water can be completely removed from the intermediate layer by heating, without the accessible surface of the clay mineral becoming appreciably lower.
  • clay minerals with magnesium ions in the octahedron layer (hectorites)
  • the elementary clay sheets are very small and hardly any stacking occurs. These clay minerals can be heated to a temperature of 600°C without any appreciable loss of accessible surface. With zinc as octahedron ion, the elementary sheets are greater. Such clay minerals already exhibit a lower accessible surface upon heating at 500°C.
  • Clay minerals with cobalt ions or nickel ions in the octahedron layer have an accessible surface and thermal stability in-between those of magnesium- and zinc-containing clay minerals.
  • Synthetic clay minerals are hydrophilic, as are natural clay minerals.
  • organic compounds capable of entering into a hydrogen bridge bond with the surface of the clay sheets.
  • organic chemical compounds are known; preferably, according to the invention, compounds having one or more hydroxyl groups or primary amines are used.
  • Other suitable compounds are mentioned, for instance, in EP-A 0 747 322.
  • the above clay materials according to the invention also lend themselves eminently for providing polymerization catalysts. After polymerization, the elementary sheets are then eminently distributed in the polymer and the properties of the polymer are optimally influenced.
  • the following preferred embodiment of the material according to the invention is used.
  • Positively charged colloidal particles or clusters of compounds of alkaline reaction are applied to the surface of the clay sheets. Owing to the negative charge of the clay sheets, application can be effected by exchange.
  • WO-A 9607613 a method has been described to prepare Al ⁇ 3 clusters with a high concentration and subsequently to apply them to the clay sheets.
  • clay minerals with non-stacked sheets on which Al ⁇ 3 complexes have been provided by exchange are eminently suitable to improve the mechanical properties of polymers, to reduce the permeability to foreign molecules and to react with hydrogen chloride being released.
  • elementary particles are used whose surface is covered with an organic compound which prevents the adsorption of water vapor and which is compatible with the (often hydrophobic) polymers.
  • organic compound which prevents the adsorption of water vapor and which is compatible with the (often hydrophobic) polymers. Examples include a hydrogenated fatty acid triglyceride, a fatty acid, an alkali metal salt of a fatty acid, a silicone compound or the titanium equivalent of a silicone compound.
  • the organic material is preferably applied to the surface of the elementary particles under such conditions that no water vapor can condense on the surface.
  • extremely finely divided inorganic powder can be included in a non-aqueous liquid and the mixture thus obtained can be treated mechanically, whereby conglomerates of elementary particles, if any are present, are broken down.
  • mechanical treatment known methods can be used, such as colloid mills.
  • Ultrasound treatment can also be used to great advantage.
  • the extremely finely divided inorganic powder preferably after it has been covered with a suitable compound which counteracts the interaction with water, is combined with other compounds, such as beta-diketones, which improve the stability of the polymer against discoloring.
  • the starting material is a commercial aluminum oxide powder marketed by Degussa. It is Alon-C, aluminum oxide with a surface area of 80 to 100 m 2 per gram, consisting of elementary particles of approximately 50 nm.
  • the powder which has been exposed to the air is heated under vacuum at 90 tot 100°C for one hour to remove water, if any has been absorbed.
  • the thus pretreated powder is introduced at approximately 50 to 70°C into hardened soybean oil or sunflower oil.
  • the weight ratio of the fat and the oxide is approximately three.
  • the melting point of the hardened fat is 30 to 40°C, whereafter the thus obtained mixture is intensively agitated with an UltraTurrax.
  • the resultant mixture is applied as particles of dimensions of 1 to 2 mm in molten form to a cooled moving aluminum plate on which the material solidifies. The thus obtained solid particles are finally removed from the aluminum plate.
  • the' starting material is magnesium nitrate, which is allowed to react with ammonium oxalate to form insoluble magnesium oxalate. After separation of the liquid and washing of the precipitate, the solid substance is dried at 120°C.
  • the magnesium oxalate is charged to a reactor through which a dried air stream is passed, and the water of crystallization is removed at about 150°C. Then the temperature is raised to about 250°C, whereby the dehydrated magnesium oxalate decomposes to carbon dioxide and magnesium oxide. After cooling in the dried air stream, the solid substance is included in molten hydrogenated fat. During transfer, contact with atmospheric air is avoided to prevent absorption of water by the magnesium oxide. The weight ratio of the fat and the oxide is approximately three. The melting point of the hardened fat is 30 to 40°C, whereafter the thus obtained mixture is intensively agitated with an UltraTurrax. Finally, the resultant mixture is applied as particles of dimensions of 1 to 2 mm in molten form to a cooled moving aluminum plate on which the material solidifies. The thus obtained solid particles are finally removed from the aluminum plate.
  • Amounts of 0.2, 0.3 and 0.5% by weight of the above- discussed mixtures of hardened fat and aluminum oxide or magnesium oxide are mixed with polyvinyl chloride granules in a Nauta mixer. After thorough mixing, the mixture is extruded to form rectangular sheets of a thickness of about 1 mm and dimensions of 3x20 cm.
  • these sheets are placed in an oven maintained at 150°C.
  • the oven can contain 10 sheets.
  • the sheets are pulled from the oven at a rate of 1 cm per hour.
  • the front portion of the sheet is exposed to the high temperature for about one hour and the rear portion for about 20 hours.
  • Stabilization by the powder is indicated by the length of the sheets that is discolored.
  • a sheet without stabilizing powder is also pulled from the oven.

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  • 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)

Abstract

Cette composition polymère résistante à la décoloration et à la libération par dissociation de composés acides corrosifs comprend au moins un polymère thermoplastique dans lequel est dispersée de forme homogène une substance inorganique solide à réaction alcaline constituée de particules élémentaires d'une grandeur inférieure à 0,5 νm. L'invention concerne également l'utilisation de cette substance solide dans des compositions polymères.
PCT/NL1998/000463 1998-01-08 1998-08-14 Composition polymere WO1999035184A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU87532/98A AU8753298A (en) 1998-01-08 1998-08-14 Polymer composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
NL1007985 1998-01-08
NL1007985A NL1007985C2 (nl) 1998-01-08 1998-01-08 Polymeersamenstelling.
NL1008741 1998-03-27
NL1008741 1998-03-27

Publications (1)

Publication Number Publication Date
WO1999035184A1 true WO1999035184A1 (fr) 1999-07-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005007757A2 (fr) * 2003-07-18 2005-01-27 Engelhard Corporation Precurseurs de revetement poudreux et leur utilisation dans des compositions de revetement poudreux

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0189899A2 (fr) * 1985-01-29 1986-08-06 Kyowa Chemical Industry Co., Ltd. Composition de résine synthétique ayant une tendance réduite à la corrosion et à la coloration
EP0256872A2 (fr) * 1986-08-14 1988-02-24 Kyowa Chemical Industry Co., Ltd. Composition à base de chlorure de polyvinyle stabilisée
EP0432495A1 (fr) * 1989-11-16 1991-06-19 Kyowa Chemical Industry Co., Ltd. Composition de résine stabilisée contenant de l'halogène
EP0623555A1 (fr) * 1993-05-06 1994-11-09 Kabushiki Kaisha Kaisui Kagaku Kenkyujo Composition de résine stabilisée contenant de l'halogène, oxide de métal composé et procédé pour leur production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0189899A2 (fr) * 1985-01-29 1986-08-06 Kyowa Chemical Industry Co., Ltd. Composition de résine synthétique ayant une tendance réduite à la corrosion et à la coloration
EP0256872A2 (fr) * 1986-08-14 1988-02-24 Kyowa Chemical Industry Co., Ltd. Composition à base de chlorure de polyvinyle stabilisée
EP0432495A1 (fr) * 1989-11-16 1991-06-19 Kyowa Chemical Industry Co., Ltd. Composition de résine stabilisée contenant de l'halogène
EP0623555A1 (fr) * 1993-05-06 1994-11-09 Kabushiki Kaisha Kaisui Kagaku Kenkyujo Composition de résine stabilisée contenant de l'halogène, oxide de métal composé et procédé pour leur production

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005007757A2 (fr) * 2003-07-18 2005-01-27 Engelhard Corporation Precurseurs de revetement poudreux et leur utilisation dans des compositions de revetement poudreux
WO2005007757A3 (fr) * 2003-07-18 2005-06-23 Engelhard Corp Precurseurs de revetement poudreux et leur utilisation dans des compositions de revetement poudreux
US7335695B2 (en) 2003-07-18 2008-02-26 Engelhard Corporation Powder coating precursors and the use thereof in powder coating compositions
AU2004257294B2 (en) * 2003-07-18 2010-07-15 Basf Catalysts Llc Powder coating precursors and the use thereof in powder coating compositions

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