EP1675889A2 - Procede de production de plastiques contenant des charges - Google Patents

Procede de production de plastiques contenant des charges

Info

Publication number
EP1675889A2
EP1675889A2 EP04790022A EP04790022A EP1675889A2 EP 1675889 A2 EP1675889 A2 EP 1675889A2 EP 04790022 A EP04790022 A EP 04790022A EP 04790022 A EP04790022 A EP 04790022A EP 1675889 A2 EP1675889 A2 EP 1675889A2
Authority
EP
European Patent Office
Prior art keywords
filler
production
precursor
plastic
fillers
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.)
Withdrawn
Application number
EP04790022A
Other languages
German (de)
English (en)
Inventor
Stefan Kaskel
Ullrich Holle
Holger Althues
Regina Palkovits
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.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
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 Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of EP1675889A2 publication Critical patent/EP1675889A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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

Definitions

  • the present invention relates to a process for the production of plastics containing fillers, in particular it relates to a process for the production of transparent molded articles containing fillers.
  • Inorganic fillers are used to change or coordinate mechanical and chemical properties e.g. to reduce the flammability of polymers and plastics.
  • transparent plastics have been difficult to modify with inorganic fillers without the plastic becoming cloudy because inorganic particles with a diameter> 300 nm or aggregates of smaller particles lead to light scattering effects which cause the plastic to become cloudy.
  • Small inorganic particles ⁇ 300 nm, nanoparticles, which are separated from each other within the plastic, only lead to minor scattering effects, so that the transparency of the plastic is retained.
  • the aim of the present invention is to develop a generally applicable process which allows the production of inorganic nanoparticles within plastics, the s / ⁇ u generation being used within a microemulsion in which the monomer required for producing the plastic forms the oil phase of the microemulsion ,
  • Inorganic fillers have long been used to modify the physical and chemical properties of plastics. In the past few years in particular
  • the particles have to be surface modified, which in part leads to high costs if, for example, functionalized silanes are used.
  • Another disadvantage is that the particles must first be isolated.
  • the Aerosil process or the microemulsion method allows the production of inorganic nanoparticles, but subsequent isolation steps such as drying and thermal treatment in the case of the microemulsion method lead to aggregates or sintering together of the primary particles, which makes it difficult or even impossible to disperse the particles into the organic matrix.
  • the second strategy uses, for example, functionalized monomers or block groups such as POSS (polyhedral oligomeric silsesquioxane), which are either integrated as such into the polymer or are further reacted during the polymerization in a sol-gel reaction, with the spatial separation of the functionalized monomers a homogeneous distribution of the inorganic phase is achieved.
  • POSS polyhedral oligomeric silsesquioxane
  • the homogeneous, molecular distribution of the inorganic component leads to transparent plastic glasses, but the inorganic components do not show the physical properties that are characteristic of inorganic nanoparticles and thus do not allow the introduction of a function such as luminescence in semiconductors, which is used for the inorganic bulk phase or the like Is characteristic of nanoparticles.
  • the uncontrolled formation of aggregates or phase separation leads to clouding of the plastic, so that no transparent plastics can be obtained.
  • the object of the present invention was accordingly to provide a process for the production of plastics containing fillers which does not have the disadvantages listed above.
  • the method is intended to enable the production of transparent plastics, the transparency of which is not or only barely visibly reduced by adding the fillers to the pure plastic.
  • the present invention accordingly relates to a process for the production of plastics containing fillers, which is characterized in that a reactive precursor of the filler of the polymer precursor is mixed, the reactive precursor of the filler is converted into the filler and - the polymer precursor is polymerized to give the plastic.
  • the fillers are first formed in situ, preferably in the aqueous phase of a w / o microemulsion or miniemulsion.
  • the fillers produced have a particle size in the nanometer range and are evenly distributed in the preliminary stage and thus also in the finished plastic.
  • the appearance of the finished plastic, e.g. B. the transparency, is not impaired even with relatively high layer thicknesses.
  • the polymer precursor is in a mini or micro emulsion.
  • the micelles usually have a diameter of up to approx. 100 nm, preferably up to 50 nm, in particular up to 20 nm. Emulsions with larger micelles are less preferred because light scattering effects can occur.
  • the monomer forms or is contained in the oil phase.
  • This emulsion can also be referred to as an inverse emulsion, since the main phase is formed by the oil phase and not by the aqueous phase as is otherwise the case with emulsions.
  • the reactive precursor of the filler is mixed with that of a w / o microemulsion or miniemulsion of a liquid polymer precursor or a solution of the polymer precursor.
  • the reactive precursor for the filler is in the aqueous phase and preferably reacts with the water, for example by hydrolysis, or by precipitation reaction with a compound, such as a salt, which is present or supplied in the aqueous phase to form the filler.
  • This embodiment has the advantage that the reactive precursor of the filler is evenly distributed in the monomer and consequently also in the end product.
  • polymer precursor is to be understood as meaning liquid or soluble polymerizable monomers, oligomers or polymers which can be converted into the finished polymer by customary polymerization reactions.
  • Monomers and oligomers or mixtures of monomers and / or oligomers are preferably used for the production of copolymers.
  • Particularly preferred polymer precursors are those which lead to transparent end products.
  • Suitable monomers are acrylic acid and its derivatives and their salts, methacrylic acid and their salts, styrene and alkenes, ethylene terephthalic acids and ethylene terephthalic acid, precursors of polycarbonates, polyepoxides, ethylene-norbornene copolymers and any copolymers of the corresponding monomers.
  • the fillers are preferably selected from inorganic compounds, in particular from hydroxides, oxides, sulfides, phosphates, carbonates, fluorides, particularly preferably from Mg (OH) 2 , MgeAI 2 (OH) 16 (CO 3 ), SiO 2 , TiO 2 , ZrO 2 , BaTiO 3 , PbZrO 3 , LiNbO 3 , zeolites, MgO, CaO, ZnO, Fe 3 O 4 , ZnS, CdS, CaCO 3 , BaCO 3 , CaSO 4 , CaF 2 , BaF 2 .
  • inorganic compounds in particular from hydroxides, oxides, sulfides, phosphates, carbonates, fluorides, particularly preferably from Mg (OH) 2 , MgeAI 2 (OH) 16 (CO 3 ), SiO 2 , TiO 2 , ZrO 2 , BaTiO 3 , PbZrO 3 , LiNbO 3
  • luminescent compounds can also be used, such as the BaF 2 , ZnO, ZnS and CdS or Y 2 O 3 , YVO 4 , Zn 2 SiO 4 , CaWO 4 , MgSiO 3 , SrAI 2 O 4 , Gd 2 O 3 S already mentioned , La 2 O 2 S, BaFCI, LaOBr, Ca 10 (PO 4 ) 6 (F, CI) 2 , BaMg 2 AI 6 O 27 , CeMgAlnO 19 and the like. ZnSe. Due to the general applicability of the method according to the invention, the inorganic component can be varied within wide limits.
  • the particles preferably have a particle size in the nanometer range.
  • the particle size of the fillers is preferably less than 300 nm, but if possible even smaller, preferably between 5 and 50 nm with a narrow size distribution.
  • a microemulsion or miniemulsion of polymer precursor, water and a surfactant is first prepared in a manner known per se.
  • Nonionic surfactants e.g. ethoxylated fatty alcohols or ionic surfactants or amphiphilic block copolymers.
  • Polymerizable surfactants can also be used for better integration of the filler particles formed.
  • the reactive precursor of the filler is then added.
  • the reactive precursor of the filler is mixed with the polymer precursor or a solution of the polymer precursor in an organic solvent.
  • Fillers which can be obtained by precipitation reactions to form sparingly soluble salts, such as, for example, ZnS, CdS, such as by introducing H 2 S into the liquid polymer precursor, or carbonates by introducing CO 2 into the liquid can also be incorporated into the process according to the invention
  • Polymer precursor phosphates which are obtained by the precipitation reaction with soluble phosphates or phosphoric acid, fluorides which can be obtained by the precipitation reaction, for example with NH 4 F, and further salts which are obtainable in this way.
  • One of the cations or anions of the salt to be produced can also be used as a counter ion of an ionic surfactant.
  • the two-emulsion technique can also be used to produce salts.
  • one component of the reagents required for the precipitation is dissolved in the aqueous phase of a w / o microemulsion, the oil phase of which consists of the corresponding monomer, and the components are reacted by combining the emulsions.
  • salts can also be dissolved within the aqueous phase of an emulsion, which, by reaction with a gas or a second microemulsion, lead to precipitation within the inverse micelles.
  • the size of the particles can be controlled in particular in emulsions, such as by the water / surfactant ratio and the choice of surfactant. This is important, for example, for controlling physical properties such as luminescence via size quantization and enables the color of a luminescent plastic glass to be specifically adjusted.
  • the polymer precursor is polymerized in a manner known per se in the presence of the filler produced in situ. If the mixture to be polymerized is in the form of a w / o emulsion, the polymerization can take place as bulk polymerization. Bulk polymerisation is suitable for the production of objects with a higher layer thickness and also for the production of products with a complex structure.
  • the polymerization can e.g. B. for the production of films can also be carried out as a so-called solution polymerization by diluting the polymer precursor in the oil phase with a suitable solvent and then polymerizing. After removing the solvent, the plastic containing the fillers can be obtained as a transparent film.
  • any filler-containing plastics can be produced.
  • the method according to the invention is particularly suitable for the production of transparent plastic glasses containing inorganic nanoparticles.
  • the mixture obtained after the production of the filler particles is placed in a mold and polymerized in the mold.
  • the mixture obtained after generation of the filler particles is applied to the surface to be coated and then polymerized.
  • the polymerization takes place at 45 ° C. in a tempered water bath within 8 hours, the sample is cured at 90 ° C. for a further 3 hours.
  • the product is a transparent polymer made of MMA with a homogeneous distribution of SiO 2 particles with a very narrow size distribution in the range of a few nanometers.
  • Example 1 The electron microscopic image of a microtome section of the plastic glass described in Example 1, which contains inorganic (SiO 2 ) nanoparticles, is shown in the attached figure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production de plastique contenant des charges, procédé selon lequel un précurseur réactif de la charge est mélangé avec le précurseur du polymère, ledit précurseur réactif de la charge est transformé en charge et le précurseur de polymère est polymérisé pour former le plastique. Les charges ainsi produites présentent une taille de particules de l'ordre du nanomètre et sont répartis uniformément dans le précurseur et également dans le plastique fini, de sorte que l'apparence du plastique, par exemple, la transparence du plastique fini, n'est pas affectée.
EP04790022A 2003-10-22 2004-10-20 Procede de production de plastiques contenant des charges Withdrawn EP1675889A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10349061A DE10349061A1 (de) 2003-10-22 2003-10-22 Verfahren zur Herstellung von Füllstoffe enthaltenden Kunststoffen
PCT/DE2004/002348 WO2005040251A2 (fr) 2003-10-22 2004-10-20 Procede de production de plastiques contenant des charges

Publications (1)

Publication Number Publication Date
EP1675889A2 true EP1675889A2 (fr) 2006-07-05

Family

ID=34484897

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04790022A Withdrawn EP1675889A2 (fr) 2003-10-22 2004-10-20 Procede de production de plastiques contenant des charges

Country Status (5)

Country Link
US (1) US20070219293A1 (fr)
EP (1) EP1675889A2 (fr)
JP (1) JP2007523222A (fr)
DE (2) DE10349061A1 (fr)
WO (1) WO2005040251A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT501471B1 (de) * 2005-06-28 2006-09-15 Tigerwerk Lack Und Farbenfabri Verfahren zur herstellung von nanoskalige zusatzstoffe nanodispers verteilt enthaltenden polyesterharzen als bindemittel für pulverlacke
JP5103723B2 (ja) * 2005-09-30 2012-12-19 住友化学株式会社 無機物粒子含有メタクリル樹脂の製造法
US10208226B2 (en) * 2015-07-23 2019-02-19 The Boeing Company Composites transmissive to visual and infrared radiation and compositions and methods for making the composites
US10353123B2 (en) * 2017-08-08 2019-07-16 Apple Inc. Electronic Devices with glass layer coatings

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1255233B (it) * 1992-07-17 1995-10-20 Himont Inc Procedimento per la stabilizzazione di polimeri olefinici
IL123468A (en) * 1998-02-26 2001-08-26 Yissum Res Dev Co Methods for the preparation of nanosized material particles
EP1064323B1 (fr) * 1998-03-16 2005-03-02 Dow Global Technologies Inc. Methode de preparation de nanocomposites polyolefiniques
US20030069332A1 (en) * 2001-09-14 2003-04-10 Giorgio Agostini Prepared elastomer/reinforcing filler composite and tire having component thereof
US6962946B2 (en) * 2001-11-21 2005-11-08 3M Innovative Properties Company Nanoparticles having a rutile-like crystalline phase and method of preparing same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005040251A2 *

Also Published As

Publication number Publication date
DE112004002597D2 (de) 2006-09-14
US20070219293A1 (en) 2007-09-20
WO2005040251A2 (fr) 2005-05-06
JP2007523222A (ja) 2007-08-16
DE10349061A1 (de) 2005-05-25
WO2005040251A3 (fr) 2005-06-16

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