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WO1994003536A1 - Poudre a base d'oxyde de calcium utile comme additif pour polymeres et son procede de preparation et d'utilisation - Google Patents

Poudre a base d'oxyde de calcium utile comme additif pour polymeres et son procede de preparation et d'utilisation Download PDF

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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
Authority
WO
WIPO (PCT)
Prior art keywords
calcium oxide
tris
propenolatomethyl
butanolate
bis
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.)
Ceased
Application number
PCT/EP1993/002062
Other languages
English (en)
Inventor
Mario Bezze
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MICROMIN Srl INDUSTRIA MICRONIZZAZIONE MINERALI
Original Assignee
MICROMIN Srl INDUSTRIA MICRONIZZAZIONE MINERALI
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
Application filed by MICROMIN Srl INDUSTRIA MICRONIZZAZIONE MINERALI filed Critical MICROMIN Srl INDUSTRIA MICRONIZZAZIONE MINERALI
Publication of WO1994003536A1 publication Critical patent/WO1994003536A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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.

Landscapes

  • 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

Une poudre à base d'oxyde de calcium anhydre, utile comme additif pour polymères et leurs mélanges, comprend des noyaux d'oxyde de calcium anhydre ainsi qu'un enrobage comprenant un agent de couplage à base de titanate ou de zirconate organique, ou de leur mélange.
PCT/EP1993/002062 1992-08-06 1993-08-03 Poudre a base d'oxyde de calcium utile comme additif pour polymeres et son procede de preparation et d'utilisation Ceased WO1994003536A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITT092A000685 1992-08-06
ITTO920685A IT1256927B (it) 1992-08-06 1992-08-06 Polvere a base di ossido di calcio, utile quale additivo per polimeri,procedimento per la sua preparazione e impiego.

Publications (1)

Publication Number Publication Date
WO1994003536A1 true WO1994003536A1 (fr) 1994-02-17

Family

ID=11410678

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/002062 Ceased WO1994003536A1 (fr) 1992-08-06 1993-08-03 Poudre a base d'oxyde de calcium utile comme additif pour polymeres et son procede de preparation et d'utilisation

Country Status (2)

Country Link
IT (1) IT1256927B (fr)
WO (1) WO1994003536A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014075197A1 (fr) 2012-11-15 2014-05-22 Kalkfabrik Netstal Ag Oxyde de calcium modifié en surface
CN118599270A (zh) * 2024-05-30 2024-09-06 江苏伊尔曼新材料有限公司 高抗水解聚酯材料及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
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 (ja) * 1985-07-05 1987-01-14 Nissan Motor Co Ltd 高浸透性シ−リング材
JPS6286037A (ja) * 1985-10-11 1987-04-20 Mitsui Toatsu Chem Inc 無機フイラ−含有ポリオレフイン樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
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 (ja) * 1985-07-05 1987-01-14 Nissan Motor Co Ltd 高浸透性シ−リング材
JPS6286037A (ja) * 1985-10-11 1987-04-20 Mitsui Toatsu Chem Inc 無機フイラ−含有ポリオレフイン樹脂組成物

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8043, Derwent World Patents Index; *
DATABASE WPI Week 8721, Derwent World Patents Index; *
PATENT ABSTRACTS OF JAPAN *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014075197A1 (fr) 2012-11-15 2014-05-22 Kalkfabrik Netstal Ag Oxyde de calcium modifié en surface
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 (fr) 2012-11-15 2018-11-07 Kalkfabrik Netstal AG Oxyde de calcium à surface modifiée et son procédé de fabrication
US10457811B2 (en) 2012-11-15 2019-10-29 Kalkfabrik Netstal Ag Surface-modified calcium oxide
CN118599270A (zh) * 2024-05-30 2024-09-06 江苏伊尔曼新材料有限公司 高抗水解聚酯材料及其制备方法和应用

Also Published As

Publication number Publication date
ITTO920685A0 (it) 1992-08-06
ITTO920685A1 (it) 1994-02-06
IT1256927B (it) 1995-12-27

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