WO2005040251A2 - Verfahren zur herstellung von füllstoffe enthaltenden kunststoffen - Google Patents
Verfahren zur herstellung von füllstoffe enthaltenden kunststoffen Download PDFInfo
- Publication number
- WO2005040251A2 WO2005040251A2 PCT/DE2004/002348 DE2004002348W WO2005040251A2 WO 2005040251 A2 WO2005040251 A2 WO 2005040251A2 DE 2004002348 W DE2004002348 W DE 2004002348W WO 2005040251 A2 WO2005040251 A2 WO 2005040251A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- filler
- production
- precursor
- plastic
- fillers
- Prior art date
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.
- 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.
- 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.
- 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
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/595,472 US20070219293A1 (en) | 2003-10-22 | 2004-10-20 | Method for the production of plastics containing fillers |
EP04790022A EP1675889A2 (de) | 2003-10-22 | 2004-10-20 | Verfahren zur herstellung von füllstoffe enthaltenden kunststoffen |
DE112004002597T DE112004002597D2 (de) | 2003-10-22 | 2004-10-20 | Verfahren zur Herstellung von Füllstoffe enthaltenden Kunststoffen |
JP2006535942A JP2007523222A (ja) | 2003-10-22 | 2004-10-20 | 充填剤含有プラスチックの製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10349061.2 | 2003-10-22 | ||
DE10349061A DE10349061A1 (de) | 2003-10-22 | 2003-10-22 | Verfahren zur Herstellung von Füllstoffe enthaltenden Kunststoffen |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005040251A2 true WO2005040251A2 (de) | 2005-05-06 |
WO2005040251A3 WO2005040251A3 (de) | 2005-06-16 |
Family
ID=34484897
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2004/002348 WO2005040251A2 (de) | 2003-10-22 | 2004-10-20 | Verfahren zur herstellung von füllstoffe enthaltenden kunststoffen |
Country Status (5)
Country | Link |
---|---|
US (1) | US20070219293A1 (de) |
EP (1) | EP1675889A2 (de) |
JP (1) | JP2007523222A (de) |
DE (2) | DE10349061A1 (de) |
WO (1) | WO2005040251A2 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007000002A1 (de) * | 2005-06-28 | 2007-01-04 | Tigerwerk Lack- Und Farbenfabrik Gmbh & Co. Kg. | Verfahren zur herstellung von nanoskalige zusatzstoffe nanodispers verteilt enthaltenden polyesterharzen als bindemittel für pulverlacke |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0581146A2 (de) * | 1992-07-17 | 1994-02-02 | Montell North America Inc. | Verfahren zur Stabilizierung von Olefin-Polymeren |
WO1999047598A1 (en) * | 1998-03-16 | 1999-09-23 | The Dow Chemical Company | Polyolefin nanocomposites |
EP1293529A2 (de) * | 2001-09-14 | 2003-03-19 | The Goodyear Tire & Rubber Company | Elastomer/Füllstoff Verbund |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL123468A (en) * | 1998-02-26 | 2001-08-26 | Yissum Res Dev Co | Methods for the preparation of nanosized material particles |
US6962946B2 (en) * | 2001-11-21 | 2005-11-08 | 3M Innovative Properties Company | Nanoparticles having a rutile-like crystalline phase and method of preparing same |
-
2003
- 2003-10-22 DE DE10349061A patent/DE10349061A1/de not_active Withdrawn
-
2004
- 2004-10-20 JP JP2006535942A patent/JP2007523222A/ja active Pending
- 2004-10-20 DE DE112004002597T patent/DE112004002597D2/de not_active Expired - Fee Related
- 2004-10-20 WO PCT/DE2004/002348 patent/WO2005040251A2/de active Application Filing
- 2004-10-20 US US10/595,472 patent/US20070219293A1/en not_active Abandoned
- 2004-10-20 EP EP04790022A patent/EP1675889A2/de not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0581146A2 (de) * | 1992-07-17 | 1994-02-02 | Montell North America Inc. | Verfahren zur Stabilizierung von Olefin-Polymeren |
WO1999047598A1 (en) * | 1998-03-16 | 1999-09-23 | The Dow Chemical Company | Polyolefin nanocomposites |
EP1293529A2 (de) * | 2001-09-14 | 2003-03-19 | The Goodyear Tire & Rubber Company | Elastomer/Füllstoff Verbund |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007000002A1 (de) * | 2005-06-28 | 2007-01-04 | Tigerwerk Lack- Und Farbenfabrik Gmbh & Co. Kg. | Verfahren zur herstellung von nanoskalige zusatzstoffe nanodispers verteilt enthaltenden polyesterharzen als bindemittel für pulverlacke |
Also Published As
Publication number | Publication date |
---|---|
DE10349061A1 (de) | 2005-05-25 |
US20070219293A1 (en) | 2007-09-20 |
DE112004002597D2 (de) | 2006-09-14 |
WO2005040251A3 (de) | 2005-06-16 |
EP1675889A2 (de) | 2006-07-05 |
JP2007523222A (ja) | 2007-08-16 |
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