WO1994003536A1 - A power based on calcium oxide, useful as an additive for polymers, and a method for the preparation and use thereof - Google Patents
A power based on calcium oxide, useful as an additive for polymers, and a method for the preparation and use thereof Download PDFInfo
- Publication number
- WO1994003536A1 WO1994003536A1 PCT/EP1993/002062 EP9302062W WO9403536A1 WO 1994003536 A1 WO1994003536 A1 WO 1994003536A1 EP 9302062 W EP9302062 W EP 9302062W WO 9403536 A1 WO9403536 A1 WO 9403536A1
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- WO
- WIPO (PCT)
- Prior art keywords
- calcium oxide
- tris
- propenolatomethyl
- butanolate
- bis
- Prior art date
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- Ceased
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Definitions
- the present invention relates to a powder based on anhydrous calcium oxide which is useful as an additive for polymers, elastomers and resins, to a method for the preparation thereof, and to the use thereof in methods for the preparation of polymeric materials and articles made from these materials.
- the invention relates to a powder of anhydrous calcium oxide which is useful as a filler for rendering materials compatible and can absorb the vapours which develop during the moulding and extrusion of the materials mentioned above and, more particularly, during the mixing of polymeric materials of different chemical natures.
- a first subject of the present invention is constituted by a powder of the type specified above, characterized in that it comprises cores of anhydrous calcium oxide and a coating comprising a coupling agent based on an organic titanate or zirconate or a mixture thereof.
- the powder of the invention preferably has a particle-size distribution with granules of less than 20 microns, this dimension being suitable for rendering the micronized powder easy to disperse even in the ' thinnest fibres which may be included in the polymeric materials.
- the coating with organic titanates or zirconates is effected with layers having thicknesses at molecular level and the coating can render the powder thus treated compatible with polymers, elastomers and resins and can also render the powder impermeable to atmospheric moisture and easy to handle.
- inorganic (mineral) substance such as calcium oxide compatible with organic substances such as polymers, elastomers and resins.
- Coupling agents such as titanates and zirconates are suitable for acting as agents for rendering the substances compatible by activating addition and condensation reactions of polymers.
- this activation occurs in several polymers simultaneously, either in the absence or in the presence of fillers or reinforcements (inorganic or organic) or peroxides, the activation may give rise to repoly erisation or copoly erisation (for example, an intermolecular readjustment) or grafting, or other molecular modifications resulting in some other form of
- the organic groups of the tetrafunctional organic zirconates and titanates may be selected from a large number of organic radicals, provided that at least one of the organic groups is reactive with ' the free radicals of the polymer or mixed polymers to which the powders of the invention are added.
- Suitable organic radicals comprise saturated or unsaturated aliphatic hydrocarbon radicals and • saturated or unsaturated hydrocarbon radicals containing oxo groups.
- the useful zirconates and titanates comprise compounds of the formula ROMXYZ in which
- RO is a reactive alkoxy group
- M is titanium or zirconium
- X is a carboxylate or alcoholate group
- Y is a functional alkyl or aryl group
- Z is a reactive group, for example, an amino, thio or acryl group.
- Organic titanates or zirconates useful in the present invention comprise:
- titanium IV 2, 2 bis 2-propenolatomethyl) butanolate, tris (dodecyl) benzene sulphonate-0, titanium IV 2 , 2 (bis-2-propenolatomethyl) butanolate, tris (dioctyl) phosphate-O, titanium IV 2,2 (bis 2-propenolatomethyl) butanolate, tris (2-ethylenediamino) ethylate, titanium IV 2,2 (bis 2-propenolatomethyl) butanolate, tris (3-amino) phenylate,
- Organozirconates constituted by lower alkoxy (C ⁇ -Cg) tri(nieta)acryl zirconates such as, in particular, neopentoxytriacryl zirconate, neohexoxytriacryl zirconate, neopentoxytrimethacryl zirconate and neohexoxytri ethacryl zirconate are particularly preferred.
- the micronization of the calcium oxide preferably takes place in closed circuit in an inert atmosphere and, typically, comprises the steps of:
- the coating is carried out in a stirred high-kinetics reactor (for example, in a Henschel mixer) in an inert atmosphere, at subatmospheric pressure and, preferably, at a temperature of between 25 and 120°C with the gradual introduction of:
- the organic titanates or zirconates described above separately or in mixtures, typically in quantities of from 0.2 to 10% by weight with reference to the weight of the calcium oxide.
- any lubricating and antistatic agents such as fatty acids, amines or metal salts, preferably in percentages of from 0.5 to 10% by weight, with reference to the calcium oxide.
- the micronized calcium oxide of the invention is used as an additive for polymers such as polyethylene, copolymers of ethylene with propylene, butylene, hexene, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl me ' thacrylate, polypropylene, polybutylene, polybutadiene, polyvinyl chlorides, polystyrene, polyvinylethyl ether, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl fluoride, polyvinylidene chloride, polyesters and mixtures thereof.
- polymers such as polyethylene, copolymers of ethylene with propylene, butylene, hexene, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl me ' thacrylate, polypropylene, polybut
- the powder is used in particular in the blending of polymeric mixtures of waste comprising polymers of various natures selected from those mentioned above, since it is suitable for performing the role of an agent for rendering different polymers compatible and also for absorbing fumes developed in the course of the blending of the polymers in the fused state.
- the quantity of organic zirconate or titanate used in the polymeric composition may vary considerably in dependence on the natures of the polymers.
- the minimum quantity of the coupling agent must be such as to bring about the formation of functional groups which are reactive with the free radicals in the polymer to give rise to the desired degree of cross-linking.
- the quantity of coupling agents introduced into the polymeric composition by means of the coated calcium oxide powder is between 0.1 and 15 parts by weight of the coupling agent per 100 parts of the polymer used, most preferably,, from 0.5 to 10 parts of the coupling agent per 100 parts of the polymer used.
- Generators of free radicals may be introduced during the blending of the polymeric fixtures and may include, for example, dicumyl pero:_.de, benzoyl peroxide, t-butyl peroctoate, t-butyl perpivalate and others such as those described in the patent US-3,646,155 the description of which is intended to be incorporated in the present description by virtue of its citation.
- the quantity of free-radical generator used in the invention may vary in dependence on the polymeric mixture in question and the minimum quantity should be such as to generate free radicals in the polymer. Generally, quantities of free-radical generator within the range of from 0.1 to one part per 100 parts of polymer are used. Particularly when the polymer is constituted by or comprises a polyester such as, for example, polyethylene terephthalate, however, it is preferable to include a condensation catalyst. The quantity of condensation catalyst is not critical and may vary from about 0.05 to about 1.0 part per 100 parts of the polymer.
- Suitable catalysts of the condensation reaction comprise dibutyltin dilaurate, dibutyltin dioctoate and others such as those described in the patents US-4,389,514 and 3,746,155, the descriptions of which are intended to be incorporated in the present description by virtue of their citation.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A powder based on anhydrous calcium oxide, useful as an additive for polymers and mixtures thereof, comprises cores of anhydrous calcium oxide and a coating comprising a coupling agent based on an organic titanate or zirconate, or mixture thereof.
Description
A POWDER BASED ON CALCIUM OXIDE, USEFUL AS AN ADDITIVE FOR POLYMERS, AND A METHOD FOR THE PREPARATION AND USE THEREOF s The present invention relates to a powder based on anhydrous calcium oxide which is useful as an additive for polymers, elastomers and resins, to a method for the preparation thereof, and to the use thereof in methods for the preparation of polymeric materials and articles made from these materials.
In particular, the invention relates to a powder of anhydrous calcium oxide which is useful as a filler for rendering materials compatible and can absorb the vapours which develop during the moulding and extrusion of the materials mentioned above and, more particularly, during the mixing of polymeric materials of different chemical natures.
The need, during the processing of polymers, to eliminate the moisture and vapours which are produced due to the temperature and to the compositions of the monomers, of the polymers and of any mineral fillers is known.
It is also known that calcium oxide powder can be used as a moisture absorbent, however:
- the fact that rapid carbonation takes place extremely easily even as a result of atmospheric humidity alone,
- the fact that it is difficult to handle because of its highly caustic and irritant characteristics, and
- the technical difficulty, due to its granulometric structure, of dispersing it uniformly even in very thin films, for example 20-30 microns thick,
have meant that, hitherto, its use has been limited to
mixtures with mineral oil and waxes with low melting points, and this has prevented its use for the aforementioned purposes.
For these reasons, a first subject of the present invention is constituted by a powder of the type specified above, characterized in that it comprises cores of anhydrous calcium oxide and a coating comprising a coupling agent based on an organic titanate or zirconate or a mixture thereof.
The powder of the invention preferably has a particle-size distribution with granules of less than 20 microns, this dimension being suitable for rendering the micronized powder easy to disperse even in the ' thinnest fibres which may be included in the polymeric materials.
The coating with organic titanates or zirconates is effected with layers having thicknesses at molecular level and the coating can render the powder thus treated compatible with polymers, elastomers and resins and can also render the powder impermeable to atmospheric moisture and easy to handle.
It is known that it is difficult to render an inorganic (mineral) substance such as calcium oxide compatible with organic substances such as polymers, elastomers and resins. Coupling agents such as titanates and zirconates are suitable for acting as agents for rendering the substances compatible by activating addition and condensation reactions of polymers. When this activation occurs in several polymers simultaneously, either in the absence or in the presence of fillers or reinforcements (inorganic or
organic) or peroxides, the activation may give rise to repoly erisation or copoly erisation (for example, an intermolecular readjustment) or grafting, or other molecular modifications resulting in some other form of
"bond" or "compatible bonds".
The organic groups of the tetrafunctional organic zirconates and titanates may be selected from a large number of organic radicals, provided that at least one of the organic groups is reactive with' the free radicals of the polymer or mixed polymers to which the powders of the invention are added.
Suitable organic radicals comprise saturated or unsaturated aliphatic hydrocarbon radicals and • saturated or unsaturated hydrocarbon radicals containing oxo groups.
For example, the useful zirconates and titanates comprise compounds of the formula ROMXYZ in which
RO is a reactive alkoxy group, M is titanium or zirconium X is a carboxylate or alcoholate group, Y is a functional alkyl or aryl group, Z is a reactive group, for example, an amino, thio or acryl group.
Organic titanates or zirconates useful in the present invention comprise:
- onoalkoxytitanates such as, in particular, titanium
IV, 2-propanolate, tris iso-octadecanoate-0 and titanium
IV; 2-propanolate, tris (dodecanoate) benzene sulphonate-0.
- coordinated titanates such as titanium IV tetrakis
2-propanolate, 2-moles (dioctyl) hydrogen phosphite adduct,
- neoalkoxytitanates such as:
titanium IV 2, 2 (bis 2-propenolatomethyl) butanolate, tris (dodecyl) benzene sulphonate-0, titanium IV 2 , 2 (bis-2-propenolatomethyl) butanolate, tris (dioctyl) phosphate-O, titanium IV 2,2 (bis 2-propenolatomethyl) butanolate, tris (2-ethylenediamino) ethylate, titanium IV 2,2 (bis 2-propenolatomethyl) butanolate, tris (3-amino) phenylate,
- zirconates of heterocyclic compounds such as:
zirconium IV 2-ethyl, 2-propenolatomethyl 1,3 propandiolate, cyclic 2,2- (bis 2 propenolatomethyl) butanolate pyrophosphate-0,0,
- neoalkoxyzirconates such as:
zirconium IV 2 , 2 (bis-2-propenolatomethyl) butanolate, tris (dioctyl) phosphate-O, zirconium IV 2 , 2 (bis-2-propenolatomethyl) butanolate, tris 2-methyl-2-propenolate-0, zirconium IV 2 , 2 (bis-2-propenolate) butanolate, tris
2-propenolate-0, zirconium IV 1,1 (bis-2-propenolatomethyl) butanolate, tris (2-aminophenylate) , zirconium IV di-neoalkanolate, di(para-aminobenzoate-O) .
Organozirconates constituted by lower alkoxy (C^-Cg)
tri(nieta)acryl zirconates, such as, in particular, neopentoxytriacryl zirconate, neohexoxytriacryl zirconate, neopentoxytrimethacryl zirconate and neohexoxytri ethacryl zirconate are particularly preferred.
It is intended that mixtures of various zirconates and titanates may be used.
The micronization of the calcium oxide preferably takes place in closed circuit in an inert atmosphere and, typically, comprises the steps of:
- crushing the CaO to dimensions of less than about 10 mm,
- introducing the dry, crushed material into a ball mill, and
- separating the particles up to 20 microns, for example, by means of a cyclone separation plant in closed circuit.
The coating is carried out in a stirred high-kinetics reactor (for example, in a Henschel mixer) in an inert atmosphere, at subatmospheric pressure and, preferably, at a temperature of between 25 and 120°C with the gradual introduction of:
a) micronized calcium oxide,
b) the organic titanates or zirconates described above, separately or in mixtures, typically in quantities of from 0.2 to 10% by weight with reference to the weight of the calcium oxide.
c) any lubricating and antistatic agents such as fatty acids, amines or metal salts, preferably in percentages of from 0.5 to 10% by weight, with reference to the calcium oxide.
The micronized calcium oxide of the invention is used as an additive for polymers such as polyethylene, copolymers of ethylene with propylene, butylene, hexene, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl me'thacrylate, polypropylene, polybutylene, polybutadiene, polyvinyl chlorides, polystyrene, polyvinylethyl ether, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl fluoride, polyvinylidene chloride, polyesters and mixtures thereof.
The powder is used in particular in the blending of polymeric mixtures of waste comprising polymers of various natures selected from those mentioned above, since it is suitable for performing the role of an agent for rendering different polymers compatible and also for absorbing fumes developed in the course of the blending of the polymers in the fused state.
The uses cited above, as well as the methods of processing plastics materials, such as extrusion and injection moulding, which use the powders described constitute another subject of the present invention.
The quantity of organic zirconate or titanate used in the polymeric composition may vary considerably in dependence on the natures of the polymers. The minimum quantity of the coupling agent must be such as to bring about the formation of functional groups which are reactive with the free radicals in the polymer to
give rise to the desired degree of cross-linking.
Typically, the quantity of coupling agents introduced into the polymeric composition by means of the coated calcium oxide powder is between 0.1 and 15 parts by weight of the coupling agent per 100 parts of the polymer used, most preferably,, from 0.5 to 10 parts of the coupling agent per 100 parts of the polymer used.
Generators of free radicals may be introduced during the blending of the polymeric fixtures and may include, for example, dicumyl pero:_.de, benzoyl peroxide, t-butyl peroctoate, t-butyl perpivalate and others such as those described in the patent US-3,646,155 the description of which is intended to be incorporated in the present description by virtue of its citation.
The quantity of free-radical generator used in the invention may vary in dependence on the polymeric mixture in question and the minimum quantity should be such as to generate free radicals in the polymer. Generally, quantities of free-radical generator within the range of from 0.1 to one part per 100 parts of polymer are used. Particularly when the polymer is constituted by or comprises a polyester such as, for example, polyethylene terephthalate, however, it is preferable to include a condensation catalyst. The quantity of condensation catalyst is not critical and may vary from about 0.05 to about 1.0 part per 100 parts of the polymer. Suitable catalysts of the condensation reaction comprise dibutyltin dilaurate, dibutyltin dioctoate and others such as those described in the patents US-4,389,514 and 3,746,155, the descriptions of which are intended to be incorporated in the present description by virtue of their citation.
Claims
1. A powder based on anhydrous calcium oxide, useful as an additive for polymers and mixtures thereof, characterized in that it comprises cores of anhydrous calcium oxide and a coating comprising a coupling agent based on an organic titanate or zirconate or a mixture thereof.
2. A powder according to Claim 1, having a granule size of less than 20 microns.
3. A powder according to Claim 1 or Claim 2, in which the coupling agent is a compound of the general formula ROMXYZ in which:
RO is a reactive alkoxy group, M is titanium or zirconium X is a carboxylate or alcoholate group, Y is a functional alkyl or aryl group, Z is a reactive group, selected from an amino, thio or acryl group.
4. A powder according to any one of Claims 1 and 2 , in which the coupling agent is a compound selected from the group consisting of:
- titanium IV, 2-propanolate, tris iso-octadecanoate-0,
- titanium IV, 2-propanolate, tris (dodecanoate) benzene sulphonate-0,
- titanium IV tetrakis 2-propanolate, 2-moles (dioctyl) hydrogen phosphite adduct,
- titanium IV 2,2(bis 2-propenolatomethyl) butanolate, tris(dodecyl) benzene sulphonate-0,
- titanium IV 2,2(bis 2-propenolatomethyl) butanolate. tris(dioctyl) phosphate-O,
- titanium IV 2,2(bis 2-propenolatomethyl) butanolate, tris (2-ethylenediamino) ethylate,
- titanium IV 2,2(bis 2-propenolatomethyl) butanolate, tris (3-amino) phenylate, zirconium IV 2-ethyl, 2-propenolatomethyl, 1,3 propandiolate, cycle of 2,2-(bis 2 propenolatomethyl) butanolate pyrophosphate-0,0,
- zirconium IV 2,2(bis-2-propenolatomethyl) .butanolate, tris (dioctyl) phosphate-O,
- zirconium IV 2 , 2(bis-2-propenolatomethyl) butanolate, tris 2-methyl-2-propenolate-0,
- zirconium IV 2,2(bis-2-propenolate) butanolate, tris 2-propenolate-0,
- zirconium IV 1,1(bis-2-propenolatomethyl) butanolate, tris (2-aminophenylate) ,
- zirconium IV di-neoalkanolate, di(para-aminobenzoate- 0).
5. A powder according to Claim 1 or Claim 2 in which the coupling agent is a (C,-Cβ) alkoxy tri(meta)acryl zirconate.
6. A powder according to Claim 5 in which the coupling agent is selected from the group consisting of neopentoxytriacryl zirconate, neohexoxytriacryl zirconate, neopentoxytrimethacryl zirconate and neohexoxytrimethacryl zirconate.
7. A powder according to any one of the preceding claims in which the quantity of the coupling agent present is from 0.2 to 10% by weight with reference to the weight of the anhydrous calcium oxide.
8. A powder according to any one of the preceding claims, also comprising a quantity of from 0.5 to 10% by weight, with reference to the anhydrous calcium oxide, of a lubricating agent.
9. A method of preparing a powder based on anhydrous calcium oxide according to any one of the preceding claims, comprising a step in which the calcium oxide is micronized in an inert atmosphere and a step in which the micronized calcium oxide is coated with an organic zirconate or titanate coupling agent in' an inert atmosphere, at a temperature of from 25 to 125 C, in a stirred reactor.
10. The use of the anhydrous calcium oxide powder according to any one of Claims 1 to 8, as an additive • for polymers or mixtures thereof.
11. A method of producing polymeric compositions by mixing one or more polymers with fillers, characterized in that a powder of coated anhydrous calcium oxide according to any one of Claims 1 to 8 is used as the filler.
12. A method according to Claim 11, in which the polymer is selected from the group consisting of polyethylenes, copolymers of ethylene with propylene, butylene, hexene, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate, polypropylene, polybutylene, polybutadiene, polyvinyl chlorides, polystyrene, polyvinylethyl ether, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl fluoride, polyvinylidene chloride, polyesters and mixtures thereof.
13. A method according to Claim 12, in which a quantity of from 0.1 to 15% by weight of the coated calcium oxide powder, with reference to the weight of the polymeric mass, is added to the polymeric mass.
14. A method of extruding or injection moulding polymeric materials comprising the addition to the polymeric material of a powder of coated anhydrous calcium oxide according to any one of Claims 1 to 8.
15. A polymeric composition comprising a powder of anhydrous calcium oxide coated with organic zirconates and/or titanates having particle dimensions of less than 20 microns.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITT092A000685 | 1992-08-06 | ||
| ITTO920685A IT1256927B (en) | 1992-08-06 | 1992-08-06 | CALCIUM OXIDE BASED POWDER, USEFUL AS A POLYMER ADDITIVE, PROCEDURE FOR ITS PREPARATION AND USE. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994003536A1 true WO1994003536A1 (en) | 1994-02-17 |
Family
ID=11410678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1993/002062 Ceased WO1994003536A1 (en) | 1992-08-06 | 1993-08-03 | A power based on calcium oxide, useful as an additive for polymers, and a method for the preparation and use thereof |
Country Status (2)
| Country | Link |
|---|---|
| IT (1) | IT1256927B (en) |
| WO (1) | WO1994003536A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014075197A1 (en) | 2012-11-15 | 2014-05-22 | Kalkfabrik Netstal Ag | Surface-modified calcium oxide |
| CN118599270A (en) * | 2024-05-30 | 2024-09-06 | 江苏伊尔曼新材料有限公司 | Highly hydrolysis-resistant polyester material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55118936A (en) * | 1979-03-06 | 1980-09-12 | Oumi Kagaku Kogyo Kk | Agent for improving compression set of vulcanized rubber |
| JPS627784A (en) * | 1985-07-05 | 1987-01-14 | Nissan Motor Co Ltd | Highly permeable sealant |
| JPS6286037A (en) * | 1985-10-11 | 1987-04-20 | Mitsui Toatsu Chem Inc | Inorganic filler-containing polyolefin resin composition |
-
1992
- 1992-08-06 IT ITTO920685A patent/IT1256927B/en active IP Right Grant
-
1993
- 1993-08-03 WO PCT/EP1993/002062 patent/WO1994003536A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55118936A (en) * | 1979-03-06 | 1980-09-12 | Oumi Kagaku Kogyo Kk | Agent for improving compression set of vulcanized rubber |
| JPS627784A (en) * | 1985-07-05 | 1987-01-14 | Nissan Motor Co Ltd | Highly permeable sealant |
| JPS6286037A (en) * | 1985-10-11 | 1987-04-20 | Mitsui Toatsu Chem Inc | Inorganic filler-containing polyolefin resin composition |
Non-Patent Citations (3)
| Title |
|---|
| DATABASE WPI Week 8043, Derwent World Patents Index; * |
| DATABASE WPI Week 8721, Derwent World Patents Index; * |
| PATENT ABSTRACTS OF JAPAN * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014075197A1 (en) | 2012-11-15 | 2014-05-22 | Kalkfabrik Netstal Ag | Surface-modified calcium oxide |
| AU2013344743B2 (en) * | 2012-11-15 | 2017-03-09 | Kalkfabrik Netstal Ag | Surface-modified calcium oxide |
| US9611175B2 (en) | 2012-11-15 | 2017-04-04 | Kalkfabrik Nestal AG | Surface-modified calcium oxide |
| EP2920248B1 (en) | 2012-11-15 | 2018-11-07 | Kalkfabrik Netstal AG | Surface-modified calcium oxide and process for producing the surface-modified calcium oxide |
| US10457811B2 (en) | 2012-11-15 | 2019-10-29 | Kalkfabrik Netstal Ag | Surface-modified calcium oxide |
| CN118599270A (en) * | 2024-05-30 | 2024-09-06 | 江苏伊尔曼新材料有限公司 | Highly hydrolysis-resistant polyester material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ITTO920685A0 (en) | 1992-08-06 |
| ITTO920685A1 (en) | 1994-02-06 |
| IT1256927B (en) | 1995-12-27 |
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