EP3638717A1 - Fibres de verre à surface modifiée pour le renforcement du béton et procédé pour leur fabrication - Google Patents

Fibres de verre à surface modifiée pour le renforcement du béton et procédé pour leur fabrication

Info

Publication number
EP3638717A1
EP3638717A1 EP18733539.3A EP18733539A EP3638717A1 EP 3638717 A1 EP3638717 A1 EP 3638717A1 EP 18733539 A EP18733539 A EP 18733539A EP 3638717 A1 EP3638717 A1 EP 3638717A1
Authority
EP
European Patent Office
Prior art keywords
alkali
hydrolysis
stable
polyelectrolyte
resistant
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Withdrawn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
EP18733539.3A
Other languages
German (de)
English (en)
Inventor
Dieter Lehmann
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.)
Leibniz Institut fuer Polymerforschung Dresden eV
Original Assignee
Leibniz Institut fuer Polymerforschung Dresden eV
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 Leibniz Institut fuer Polymerforschung Dresden eV filed Critical Leibniz Institut fuer Polymerforschung Dresden eV
Publication of EP3638717A1 publication Critical patent/EP3638717A1/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Withdrawn legal-status Critical Current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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0048—Fibrous materials
    • C04B20/0068—Composite fibres, e.g. fibres with a core and sheath of different material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/1025—Coating to obtain fibres used for reinforcing cement-based products
    • C03C25/103—Organic coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/12—General methods of coating; Devices therefor
    • C03C25/16—Dipping
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/30—Polyolefins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/323—Polyesters, e.g. alkyd resins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/326—Polyureas; Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/36—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/48—Coating with two or more coatings having different compositions
    • C03C25/50—Coatings containing organic materials only
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/42—Glass
    • C04B14/44—Treatment for enhancing alkali resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • C04B20/1033—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
    • E04C5/073—Discrete reinforcing elements, e.g. fibres

Definitions

  • the invention relates to the fields of chemistry and construction and relates surface-modified glass fibers for concrete reinforcement, as they can be used for example in textile-reinforced concretes (textile concrete).
  • glass fibers are widely used as reinforcing materials in duromer, thermoplastic and elastomeric materials / plastics - but also in construction as concrete reinforcing material.
  • Glass fibers as commercial reinforcing materials are usually made from the melt and processed into numerous products.
  • glass fibers are usually processed into roving, nonwovens, mats or fabrics.
  • aligned fibers are used. Due to the low resistance to tensile forces to accommodate tensile and / or compressive forces in concrete in addition to steel as reinforcement material increasingly textile structures, such as AR glass fibers or carbon fibers (carbon), inserted as textile fiber reinforcements. Concrete with technical textiles of such fibers as reinforcements is generally referred to as textile concrete.
  • textile fiber reinforcement is u.a. The fact that they can be arranged in the near-surface edge zone of the component, as they do not rust, in contrast to reinforcements made of structural steel and therefore require little or no concrete cover.
  • Reinforcing fibers generally affect the properties of a composite material. Glass fibers as reinforcing fibers in different qualities are commercially available as [Wikipedia.org/wiki.Glassfiber, as of: 02.01.2017]:
  • Q quartz
  • S1O2 quartz glass fiber (S1O2) for use at high temperatures of up to 1450 ° C - hollow glass fibers: glass fibers (usually E glass) with a hollow cross-section
  • R-, S- and M-glass are alkali-free and increased moisture-resistant.
  • AR glass fibers For use in textile-reinforced concretes, AR glass fibers have been specifically developed and used, which have a better alkaline stability compared to E glass fibers, but as current publications show, they are also damaged by alkaline attack [Orlovski dissertations on the durability of AR- Glass Reinforcement in Textile Concrete ", Diss. RWTH Aachen, 2004 and Scheffler" For the Evaluation of AR Glass Fibers in an Alkaline Environment ", Diss. TU Dresden, 2009].
  • the size formulations are prepared as a multicomponent or multicomponent mixture in the form of an aqueous dispersion in the one-pot processing system and processed in this way.
  • the glass fibers are wetted in the manufacturing process via a dipping roll with sizing and the individual filaments usually bundled into rovings.
  • the application of sizing also achieves a certain cohesion of the glass fiber filaments in the roving.
  • the respective sizing composition is adjusted so that an optimal bonding of the structural elements is achieved, in which the roving is incorporated.
  • Today's sizing formulations are mostly "black-box" systems, ie there is little or no publicly available information on the ingredients and their formulation.
  • Slanted glass fibers usually have excellent slipperiness or lubricity with a minimum of wear or broken ends.
  • organosilazo-modified polyazamides the preparation and use of which are known, have a secondary and / or tertiary amino group and a carboxamide group in their skeleton and are bonded to a silicon atom via a polyvalent organic group.
  • the polyazamides which are polar and hygroscopic, are prepared via a Michael addition reaction or haloalkylation.
  • this Example 54 states that the glass surfaces, and derived therefrom, glass fibers treated with polyethylene 1200 molecular weight and unmodified polyazamide and subsequently reacted with epoxy resin, do not form a (hydrolysis) stable composite in water and consequently as surface modifying agents Glass fibers are unsuitable.
  • sizing to glass fibers during the processing of the sized glass fibers by the formation of protective layers should prevent filament damage, such as glass fiber breakage and abrasion. Furthermore, the sizing establishes contact between the individual glass filaments and ensures the merging of the filaments into a workable thread. Therefore, the sizing must be distributed on the glass fiber surface and should retain an "adhesive" effect after drying.
  • the size is applied to the individual glass filaments by means of a sizing roll, wherein the solids of the sizing must not have a tendency to agglomerate.
  • the glass fiber size should act as an additional diffusion barrier, which is why it should be stable even at higher pH values.
  • the SEM images of Figs. 1 and 2 exemplify that sizing does not form a closed film on the glass fiber, but the size of the dispersion during glass fiber production is only locally, i. is present at points distributed on the glass fiber surface adsorbed.
  • the predominant fiberglass surface is therefore unmodified as free / "bare" glass fiber, representing the problem of alkali resistance in the application of E-glass fibers as the standard fiber with the largest market share and also AR glass fibers in textile concrete.
  • AR glass fibers which are developed and used in particular for reinforcing plaster, screed, concrete or mortar, lose their long-term release in cementitious binders with high pH values when stored in water, according to Orlowsky [Diss. RWTH Aachen, 2004] due to the following damage mechanisms ... in cementitious binder "on strength:
  • the object of the present invention is to provide surface-modified glass fibers for concrete reinforcement, which are at least substantially protected against an alkaline attack by the lime hydrates released in the cement reaction and / or dissolution and leaching processes generated thereby, and the disclosure of a simple and inexpensive process for Preparation of such surface-modified glass fibers.
  • the surface-modified concrete strengthening glass fibers according to the invention are at least partially covered with a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or with a hydrolysis-stable and alkali-resistant polyelectrolyte complex and via (polyelectrolyte) complex formation by ionic bonding to the glass fiber surface with formation of the hydrolysis-stable and alkali-resistant polyelectrolyte complex A, wherein at least one further (co) polymer at least partially covers the polyelectrolyte complex A and is coupled to the polyelectrolyte complex A via ionic and / or covalent bonds.
  • hydrolysis-stable and alkali-resistant polyelectrolyte complex A is present, which
  • hydrolysis-stable and alkali-resistant polyelectrolyte complex A which has formed on the glass fiber surface essentially completely or completely covers the glass fiber surface and / or the further (co) polymer essentially completely or completely covers the polyelectrolyte complex A.
  • hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture a hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture
  • PolyDADMAC Polydiallyldimethylammoniumchlorid
  • Cationically modified maleimide copolymer prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylaminoalkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or
  • Amino groups and / or quaternary ammonium groups and amide groups which are chemically modified by acylation reactions of amino groups for the amide with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond,
  • At least one anionic polyelectrolyte or an anionic polyelectrolyte mixture without and / or with at least one further, different from the anionic group reactive as functionalities on the attached to the glass fiber surface hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte / or activatable functional group and / or having at least one olefinically unsaturated double bond.
  • (a) (meth) acrylic acid copolymers which are present without and / or with at least one further reactive and / or activatable functional group which has been introduced via the copolymerization, and / or which are at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of the (meth) acrylic acid group, are present, and which are preferably water-soluble, and / or
  • modified maleic acid (anhydride) copolymers which are preferably present in the acid and / or monoester and / or monoamide and / or water-soluble imide form and / or which are present without and / or with residual anhydride groups and / or, which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization, and / or which have at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, which has a polymer-analogous Implementation / modification of maleic acid (anhydride) groups are coupled, are present, and which are preferably water-soluble, and / or
  • modified itaconic acid (anhydride) (co) polymers which are preferably in the acid and / or monoester and / or monoamide and / or water soluble imide form and / or those which have no and / or residual Anhydride groups are present and / or which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization, and / or, with at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of itaconic acid (anhydride) groups, are present, and which are preferably water-soluble, and / or
  • modified fumaric acid copolymers which are preferably present in the acid and / or monoester and / or monoamide form and / or those which have no and / or at least one further reactive and / or activatable functional group which exceeds the Copolymerization is present, and / or, which are present with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of fumaric acid groups, and which are preferably water-soluble, and or
  • anionically modified (meth) acrylamide (co) polymers which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization and / or which have at least one another reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which are coupled via a polymer-analogous reaction / modification of the (meth) -acrylamide group, are present, and which are preferably water-soluble, and / or
  • sulfonic acid (co) polymers such as styrenesulfonic acid (co) polymers and / or vinylsulfonic acid (co) polymers in acid and / or salt form, which can be reacted with at least one further reactive and / or activatable polymer functional group which has been introduced via the copolymerization, and / or, with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, via a polymer-analogous reaction / modification of sulfonic acid groups such as Sulfonklamid phenomenon coupled, are present, and which are preferably water-soluble, and / or
  • hydrolysis-stable and alkali-resistant cationic polyelectrolytes or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture have a molecular weight of less than 50,000 daltons, preferably in the range of between 400 and 10,000 daltons.
  • At least one, at least difunctional and / or difunctionalized, oligomeric and / or macromolecular (co) polymer having functional groups and / or olefinic unsaturated double bonds is present as further (co) polymer.
  • thermoplastics and / or duromers and / or elastomers are present as further (co) polymer.
  • thermosetting (co) polymers polyester resins (UP resins), vinyl ester resins and epoxy resins, and as thermoplastic (co) polymers polyurethane, polyamide and polyolefins, such as polyethylene or polypropylene, and PVC be present, the polyolefins are grafted with (meth) acrylic acid derivatives and / or maleic anhydride present.
  • a hydrolysis-stable and alkali-resistant polyelectrolyte complex A is present on plain and silane-free glass fiber surfaces having at least partially covering functional groups and / or olefinically unsaturated double bonds and after reaction with functional groups and / or olefinically unsaturated double bonds chemically covalent bonds coupled with other (co) polymers present.
  • At least one, at least difunctional and / or difunctionalized, oligomeric and / or macromolecular (co) polymer having functional groups and / or olefinic unsaturated double bonds is present as further (co) polymers.
  • thermoplastics and / or duromers and / or elastomers are present as (co) polymer.
  • hydrolysis-stable cationic polyelectrolyte are amino groups, preferably primary and / or secondary amino groups, and / or quaternary ammonium groups.
  • a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges at least partially covered, wherein hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess be applied to cationic charges, and subsequently at least one additional (co) polymer on
  • polyelectrolytes which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation or are used as hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures are polyelectrolyte mixtures which are not subsequently alkylated after preparation and / or are used as the hydrolysis-stable and alkali-resistant cationic polyelectrolytes acylated and / or sulfamidated are used.
  • PolyDADMAC Polydiallyldimethylammoniumchlorid
  • Cationically modified maleimide copolymer prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylaminoalkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or
  • hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic ones are used Polyelectrolyte mixtures and / or hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges in a concentration of not more than 5 wt .-% in water or in water with the addition of acid, such as carboxylic acid, for example formic acid and / or acetic acid and / or mineral acid, without further Simple or sizing ingredients and / or silanes used.
  • acid such as carboxylic acid, for example formic acid and / or acetic acid and / or mineral acid
  • hydrolysis-stable and alkali-resistant cationic polyelectrolytes which are not post-alkylated and / or acylated and / or sulfamidated after preparation and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures which are not subsequently alkylated and / or acylated after preparation and / or acylated are sulfamidated, used in a concentration ⁇ 2 wt .-% and particularly preferably ⁇ 0.8 wt .-%.
  • a modified hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture which (s) after the preparation in a subsequent reaction partially alkylated and / or acylated and / or reacted with carbonic acid derivatives and / or sulfamidated and thus provided with a substituent with reactive and / or activatable groups for a coupling reaction, subsequently with the reactive and / or activatable groups of the covalently coupled substituent without crosslinking of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture via at least one functional group and / or via at least one olefinically unsaturated double bond is reactively reacted with other materials to form a composite material.
  • the partial alkylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture is accompanied by introduction of substituents with reactive groups by haloalkyl derivatives and / or (epi-) halohydrin and / or epoxy compounds and / or or compounds which undergo a Michael analogue addition, such as advantageously acrylates and / or acrylonitrile with amines.
  • hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges in water, preferably in the form of ammonium compounds, are used Case of primary and / or secondary and / or tertiary amino groups to the aqueous solution of carboxylic acid (s) and / or mineral acid (s) are added to convert the amino groups in the ammonium form.
  • modified glass fiber surfaces which are at least partially and preferably completely covered with at least one hydrolysis-stable and alkali-resistant cationic polyelectrolyte or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic or anionic charges, directly after their preparation and coating / surface modification and / or reactively reacted later with other materials to form chemically covalent bonds. It is also advantageous if the modified glass fiber surfaces are wound up and / or temporarily stored as a roving and subsequently reacted reactively with other materials to form chemically covalent bonds.
  • hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic or anionic charges reactive groups in the form of functional groups and / or olefinically unsaturated double bonds which are reactively reacted with functionalities of the other materials to form chemically covalent bonds.
  • the solution according to the invention makes it possible for the first time to specify surface-modified glass fibers for concrete reinforcement which are at least substantially protected against alkaline attack by the lime hydrates released in the cement reaction and / or dissolution and leaching processes generated thereby, as well as a simple and cost-effective method of production specify such surface-modified glass fibers.
  • Such surface-modified glass fibers for concrete reinforcement not only have improved properties as a whole, but are particularly suitable for further processing into textile concrete, since they have a high resistance to alkali in textile concrete.
  • Such surface-modified glass fibers can be produced as a strand or tape material.
  • surface-modified glass fibers for concrete reinforcement which are at least partially covered with at least one hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or with a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charge.
  • Complex formation are coupled by ionic bonding to the glass fiber surface to form the polyelectrolyte complex A, and wherein at least one further (co) polymer at least partially covers the polyelectrolyte complex A and is coupled to the polyelectrolyte complex A alkali-resistant via ionic and / or covalent bonds.
  • a hydrolysis-stable and alkali-resistant cationic polyelectrolyte is to be understood as meaning all the polyelectrolytes which are resistant to hydrolysis and / or alkali and have cationic charges and are colloquially also referred to as polycations.
  • a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture is to be understood as meaning all mixtures of at least two or more polyelectrolytes which are hydrolysis-stable and / or alkali-resistant and have cationic charges and are also colloquially referred to as polycation mixtures.
  • Such hydrolysis-stable and / or alkali-resistant cationic polyelectrolytes or hydrolysis-stable and / or alkali-resistant cationic polyelectrolyte mixtures can advantageously be used as
  • PolyDADMAC Polydiallyldimethylammoniumchlorid
  • Cationically modified maleimide copolymer prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylaminoalkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or
  • Such functionalities on the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture affixed to the glass fiber surface may also be an anionic polyelectrolyte or an anionic polyelectrolyte mixture without and / or with at least one further reactive and / or activatable functional group other than the anionic group and / or with at least one olefinically unsaturated double bond.
  • (a) (meth) acrylic acid copolymers which are present without and / or with at least one further reactive and / or activatable functional group which has been introduced via the copolymerization, and / or which are at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of the (meth) acrylic acid group, are present, and which are preferably water-soluble, and / or
  • modified maleic acid (anhydride) copolymers which are preferably present in the acid and / or monoester and / or monoamide and / or in preferably water-soluble imide form and / or which are present without and / or with residual anhydride groups and / or which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization, and / or which have at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which has a polymer-analogous Implementation / modification of maleic acid (anhydride) groups are coupled, are present, and which are preferably water-soluble, and / or
  • modified itaconic acid (anhydride) (co) polymers which are preferably present in the acid and / or monoester and / or monoamide and / or in preferably water-soluble imide form and / or which contain no and / or are present with remaining anhydride groups and / or, which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization, and / or, with at least one further reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of itaconic acid (anhydride) groups, are present, and which are preferably water-soluble, and / or
  • modified fumaric acid copolymers which are preferably present in the acid and / or monoester and / or monoamide form and / or those which have no and / or at least one further reactive and / or activatable functional group which exceeds the Copolymerization is present, and / or, which are present with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of fumaric acid groups, and which are preferably water-soluble, and or
  • anionically modified (meth) acrylamide (co) polymers which are present without and / or with at least one further reactive and / or activatable functional group introduced via the copolymerization and / or which have at least one another reactive and / or activatable functional group and / or with at least one olefinically unsaturated double bond which are coupled via a polymer-analogous reaction / modification of the (meth) -acrylamide group, are present, and which are preferably water-soluble, and / or
  • sulfonic acid (co) polymers such as styrenesulfonic acid (co) polymers and / or vinylsulfonic acid (co) polymers in acid and / or salt form, which can be reacted with at least one further reactive and / or activatable polymer functional group which has been introduced via the copolymerization, and / or, with at least one further reactive and / or activatable functional group and / or at least one olefinically unsaturated double bond, via a polymer-analogous reaction / modification of sulfonic acid groups such as Sulfonklamid phenomenon coupled, are present, and which are preferably water-soluble, and / or
  • hydrolysis-stable and alkali-resistant cationic polyelectrolytes present in the surface-modified glass fibers according to the invention or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture advantageously have a molecular weight below 50,000 daltons, preferably in the range between 400 and 10,000 daltons.
  • At least partially covering hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures are preferably present on the glass fiber surface.
  • hydrolysis-stable and alkali-resistant polyelectrolyte complex A which has been formed by (polyelectrolyte) complex formation and is coupled to the glass fiber surface by ionic bonding.
  • the glass fiber surface is at least partially covered by an excess of cationic charges with a hydrolysis-stable and alkali-resistant polyelectrolyte complex formed before application to the glass fiber surface.
  • a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges are according to the invention all polyelectrolyte complex compounds which have been prepared from at least one cationic polyelectrolyte and at least one anionic polyelectrolyte and which have an excess of cationic charges, and colloquially as "asymmetric Polyelektrolytkomplexe
  • These hydrolysis-stable and alkali-resistant polyelectrolyte complexes are stable to hydrolysis under the respective processing conditions and, due to their composition and macromolecule structure (s), are soluble or dissolved in water and do not form gelatinous structures.
  • This hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges formed before application to the glass fiber surface forms with the anionic glass fiber surface a hydrolysis-stable and alkali-resistant polyelectrolyte complex A which is formed by (polyelectrolyte) complex formation and coupled to the glass fiber surface by ionic bonding.
  • a hydrolysis-stable and alkali-resistant polyelectrolyte complex A according to the invention should therefore be understood as meaning a polyelectrolyte complex which:
  • polyelectrolyte complexes are composed of the anionically charged glass fiber surface and the hydrolysis-stable material applied thereto and alkali-resistant cationic polyelectrolyte and / or polyelectrolyte mixture and / or polyelectrolyte complex with an excess of cationic charges during or after the preparation of the glass fibers by complex formation and are hereinafter also referred to as polyelectrolyte complex A.
  • the polyelectrolyte complex A according to the invention thus always formed with the glass fiber surface.
  • the hydrolysis-stable and alkali-resistant polyelectrolyte complex A should substantially or completely cover the glass fiber surface as much as possible.
  • At least one further (co) polymer is present on the glass fiber which at least partially covers the polyelectrolyte complex A and is coupled to the polyelectrolyte complex A via ionic and / or covalent bonds.
  • At least one, at least difunctional and / or difunctionalized, low molecular weight and / or oligomeric and / or (co) polymer having the same or different functional groups and / or olefinic unsaturated double bonds may be present, such as advantageously thermoplastics and / or duromers and / or elastomers.
  • the at least one further (co) polymer which is formed during or after the addition and / or attached as (co) polymer, should cover the polyelectrolyte complex A substantially completely or as completely as possible.
  • At least partial coverage means a degree of coverage of at least more than 50% of the glass fiber surface and / or the glass fiber bundle surface by the polyelectrolyte complex A and also by the further (co) polymers, wherein according to the invention at least 80% and preferably 100% % coverage is to be achieved and achieved.
  • Polyelectrolyte complex A has been formed by a complex formation between the glass fiber surface and at least one hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charge, and then at least partially, substantially completely or completely the glass fiber surface.
  • the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charge is a starting material for the process according to the invention and is prepared before use in the process according to the invention.
  • polyelectrolyte complex A between the polyelectrolyte complex A and an anionic polyelectrolyte and / or an anionic polyelectrolyte mixture and / or a polyelectrolyte complex with an excess of anionic charges and cover the polyelectrolyte complex A at least partially, substantially completely or completely, and / or
  • the glass fiber surfaces at least partially covered according to the invention with the polyelectrolyte complex A are at least partially covered with at least one further (co) polymer and coupled via ionic and / or covalent bonds.
  • the preferably complete covering with at least one further (co) polymer can be carried out on the individual glass fiber and preferably on glass fibers in a glass fiber bundle / glass fiber roving via the addition of a hydrolysis-stable and alkali-resistant (co) polymer or a hydrolysis-stable and alkali-resistant (co-) Polymer mixture having functional groups which are capable of a coupling reaction by covalent bonds with the surface of the polyelectrolyte complex A, by a cohesive, at least partially, advantageously complete Unnnantelantelung / covering the surface of the polyelectrolyte complex A or the glass fiber bundle / Glasmaschinerovings done.
  • the cladding / covering of the glass fibers or of the glass fiber roving can take place by means of at least one further layer, as a result of which an alkali-resistant reinforcing material is present / arises.
  • the surface of non-alkali-resistant glass fibers by an at least partially, advantageously as complete or complete coverage by a polyelectrolyte I and at least one other (co) polymer, the ionic and / or covalent bonds and cohesively is coupled to the glass fiber surface, at least substantially fully protected against alkaline attack by the concrete matrix environment and thus processing-stable and easy to handle reinforcing materials for textile concretes are present and can be produced.
  • glass fiber ends created by fracture or cutting / cuts and / or surfaces locally damaged by handling may locally undergo an alkaline attack, this attack is limited to these locations only and does not migrate farther along the fiber surface since the covering is coupled cohesively on the glass fiber surface via ionic and / or covalent bonds, so that no continuous damage in the so modified glass fiber bundle / Glasmaschineroving can be done.
  • Such a material bond between glass fiber surface and a cladding / covering according to the invention is not known in the prior art and does not exist in the known commercially available sized glass fibers, even if they were subsequently further surface-coated in a commercial manner.
  • the size after covering from the dispersion during glass fiber production is only local, i. selectively dispersed on the glass fiber surface, since coverage to the glass fiber is thus practically only localized via the sizing sites, i. punctually / locally and not over the entire surface and can not take place cohesively.
  • the commercial sizing components that have been applied from a water dispersion are at least partially swellable, thereby lowering the mechanical strength between the glass fiber surface and the sizing material.
  • the alkali resistance of the otherwise non-alkali-resistant glass fiber is due to the inventive dense cohesive, as completely as possible blanketing / covering the glass fiber surface without loose and / or swellable structures and / or capillaries and / or cavities for the diffusion of Moisture and / or dissolved alkaline agents in the boundary layer to the glass fiber surface achieved.
  • the inventive tight cohesive, completely covering as possible cover / cover on the anionic glass fiber surface act as a kind of buffer, so that a possible alkaline attack is also buffered and thus chemically attenuated.
  • thermosetting and / or thermoplastic (co) polymers can be used.
  • thermosetting (co) polymers for example, polyester resins (UP resins), vinyl ester resins and epoxy resins can be present and used.
  • thermoplastic (co) polymers for example, polyurethane, polyolefins, e.g. Polyethylene or polypropylene, and PVC are used, the polyolefins with comonomers, such. (Meth) acrylic acid derivatives and / or maleic anhydride) modified as a copolymer and / or graft copolymer can be used.
  • the (co) polymer may also be an anionic / polyelectrolyte (mixture) or polyelectrolyte complex with an excess of anionic charges, but preferably also one or more, the modified glass fiber and / or the glass fiber strand enveloping polymers.
  • the surface-modified glass fibers according to the invention can be reactively reacted and / or coated and / or coated with oligomers and / or polymers having reactive functional groups by further chemical modification reaction with one or more low molecular weight reagents on the surface by addition and / or substitution reactions Coupled with the surface-modified glass fibers according to the invention by a (melt) reaction on the surface are coated, preferably as glass fiber roving, and further modified during processing into a textile reinforced concrete reinforcing material.
  • the (further) processing of the surface-modified glass fibers according to the invention is preferably carried out as glass fiber roving in the known pultrusion or by sheathing with a thermoplastic to form a reinforced concrete reinforcing material, wherein the coupling is preferred by reactive conversion to cohesive bonds.
  • thermoplastic or thermosetting polymer preferably takes place directly on the surface-modified glass fibers according to the invention.
  • the surface modification and encapsulation of the glass fibers and the Glasturarovings / glass fiber bundle with a thermosetting polymer can be carried out by resin impregnation in the pultrusion, preferably using epoxy resin, vinyl ester resin, polyester resin (UP resin) or polyurethane resin and partially cured depending on the type of resin and method for producing the textile reinforced concrete reinforcing materials or cured.
  • resin impregnation in the pultrusion preferably using epoxy resin, vinyl ester resin, polyester resin (UP resin) or polyurethane resin and partially cured depending on the type of resin and method for producing the textile reinforced concrete reinforcing materials or cured.
  • At least one further (protective) layer of thermosetting and / or preferably thermoplastic polymer such as, for example, polyurethane (TPU) or maleic anhydride grafted polyolefin and preferably maleic anhydride grafted polypropylene for protection against alkaline attack of the glass fibers of Glasmaschinerovings / Fiberglass bundles are applied, this layer is preferably chemically coupled and cohesively present with the duromer layer.
  • TPU polyurethane
  • maleic anhydride grafted polyolefin and preferably maleic anhydride grafted polypropylene for protection against alkaline attack of the glass fibers of Glasturarovings / Fiberglass bundles
  • this layer is preferably chemically coupled and cohesively present with the duromer layer.
  • a further surface modification and encapsulation of the glass fiber rovings / glass fiber bundles with preferably a thermoplastic polymer can be effected by sheathing the glass fibers modified as glass fiber roving / fiber bundles, for which preferably polyurethane (TPU) or polyolefin, such as polyethylene or polypropylene, for example as thermoplastic polymer, and preferably maleic anhydride-grafted polyolefin and more preferably maleic anhydride-grafted polypropylene or polyamide, such as PA6, PA66 or PA12, for protection against alkaline attack of the glass fiber is applied to the glass fiber bundle, said thermoplastic polymer layer preferably chemically coupled and cohesively bonded in contact with the surface-modified glass fibers according to the invention or the glass fiber roving / glass-fiber bundle with the surface-modified glass fibers according to the invention, and this material is present a reinforcing strand or a tape is further processed.
  • TPU polyurethane
  • polyolefin
  • the commercially produced glass fiber materials thus comprise sized glass fibers in which the glass fibers form a surface coating and a composite on the surface only at the local sizing regions and consequently can not consist of a continuous cohesive bond between the glass fiber surface and the sizing.
  • Prior art sizing or sizing niches consist of a variety of substances, some of which contain special silanes as adhesion promoter substances. Although these silanes, by reacting with the glass fiber surface, support a chemical bond between glass fiber and sizing agent, since it is formed only locally and not cohesively on the glass fiber surface, the silanes can not provide sufficient protection for the sized glass fibers.
  • the silanes usually used as alkoxysilane in sizing dispersions are known to be used in an aqueous sizing dispersion, which are not sufficiently stable over the period of use and change depending on the ambient conditions (such as temperature, pH, concentration, etc.).
  • the changes are made by reactions with each other, for example, to form Si-O-Si bonds, that is, the silanes condense with each other and possibly also with sizing (constituents) and thus chemically change as sizing (ingredient).
  • the glass fibers After application of such over time changing sizing or sizing mixtures to the glass fiber surface, which do not form a closed, cohesive surface film, the glass fibers are wound into a roving.
  • the present invention surface-modified glass fibers via the polyelectrolyte A and the other (co) polymers formed by ionic and / or covalent bonds with the polyelectrolyte complex A are coupled directly to the glass fiber surface a cohesive, flat, stable composite without capillary gaps and / or cavities for (in) diffusion of (glass) corrosive substances / media in the boundary layer / in the boundary layer area, so that no weakening of the glass fiber reinforcing effect in the composite by a corrosive / alkaline attack of liberated lime hydrate in the cement reaction and thus no damage to the glass fiber surface can be done, ie an alkaline attack is therefore not in the textile concrete.
  • the surface-modified glass fibers are produced in that a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture during or after the production of glass fibers on the glass fiber surfaces from an aqueous solution with a concentration of at most 5 wt.
  • hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges at least partially covering, wherein hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess be used on cationic charges, and subsequently at least one further (co) polymer on the de At least partially covering the resulting hydrolysis-stable and alkali-resistant polyelectrolyte complex A is applied.
  • Polyelectrolytes which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation are advantageously used as hydrolysis-stable and alkali-resistant cationic polyelectrolytes, or polyelectrolyte mixtures which are not subsequently alkylated and / or acylated after preparation as hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures / or sulfamidated.
  • hydrolysis-stable and alkali-resistant, unmodified cationic polyelectrolyte or as hydrolysis-stable and alkali-resistant, unmodified cationic polyelectrolyte mixture can advantageously
  • PolyDADMAC Polydiallyldimethylammoniumchlorid
  • Cationically modified maleimide copolymer prepared from maleic acid (anhydride) copolymer (s) and N, N-dialkylaminoalkyleneamine (s), preferably using alternating maleic acid (anhydride) copolymers, and / or
  • unmodified cationic polyelectrolytes or unmodified cationic polyelectrolyte mixtures polyethyleneimine and / or polyallylamine and / or polyamidoamine and / or cationic maleimide copolymers.
  • modified cationic polyelectrolytes or cationic polyelectrolyte mixtures can also be used.
  • strong cationic polyelectrolytes with permanent charges, such as the PolyDADMAC with quaternary ammonium groups can be independent of the pH.
  • hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or hydrolysis-stable and alkali-resistant polyelectrolyte mixtures and / or hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges in a concentration of not more than 5% by weight are advantageously dissolved in water or in water with the addition of acid.
  • acid such as carboxylic acid, for example formic acid and / or acetic acid and / or mineral acid, used without further sizing or sizing ingredients and / or silanes.
  • hydrolysis-stable and alkali-resistant cationic polyelectrolytes which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures which are not subsequently alkylated and / or acylated and / or sulfamidated after preparation , used in a concentration ⁇ 2 wt .-% and particularly preferably ⁇ 0.8 wt .-%.
  • hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolytes or hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixtures are present in a concentration of at most 5% by weight, advantageously in a concentration of ⁇ 2% by weight and particularly preferred used in a concentration ⁇ 0.8 wt .-%, wherein the concentration, depending on the nature of the hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte or hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixture, the charge density in the macromolecule, the type of cationic group (primary, secondary, tertiary amino group or quaternary ammonium group), the degree of branching and the molecular weight are each set, that is optimized, which is for the skilled person m
  • the adjustment of the concentration of hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte or hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixture also depends on whether the surface modification according to the invention is carried out directly in the glass fiber production process and / or subsequently, ie downstream.
  • the adjustment of the concentration is adapted to the respective method, whereby an overcharge in the sense of polyelectrolyte chemistry is to be avoided by excessively high concentrations.
  • Overloading then occurs or occurs due to excessively high concentrations if the packing or coverage density on the glass fiber surface is too high and the cationic polyelectrolyte molecules can not optimally arrange themselves on the glass fiber surface.
  • a rearrangement in the direction of optimum coverage density takes place with (very) slow release of the too much deposited cationic polyelectrolyte macromolecules.
  • the covering of the glass fiber surface with hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte or hydrolysis-stable, preferably unmodified, alkali-resistant cationic polyelectrolyte mixture takes place in water or in water with a solvent additive and / or acid addition, for example one or more carboxylic acids, such as formic acid and / or acetic acid, and / or mineral acids. It is particularly advantageous that for the production and further processing of the modified glass fiber surfaces according to the invention on the use of sizing or sizing components, such as silanes, can be completely dispensed with, but also with sizing modified glass fiber surfaces can be subsequently modified according to the invention.
  • a modified glass fiber surface was found which, in contrast to the statement in DE 2 315 242, Example 54, shows very good adhesion to the subsequently applied further materials and thus a very well adhering composite material can be produced and specified.
  • a modified hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture can also be used which (s) after the preparation in a subsequent reaction partially alkylated and / or acylated and / or reacted with carbonic acid derivatives and / or sulfamidized and is equipped with a substituent with reactive and / or activatable groups for a coupling reaction, which subsequently with the reactive and / or activatable groups of the covalently coupled substituent without crosslinking of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture via at least one functional Group and / or via at least one olefinically unsaturated double bond is reactively reacted with other materials to form a composite material.
  • Unmodified cationic polyelectrolytes in the context of the present invention are understood and used to mean polycations or polycation mixtures which are not chemically modified, ie alkylated (for example by halogenoalkyl), after the preparation in a subsequent reaction with low molecular weight and / or oligomeric and / or polymeric agents.
  • Derivatives and / or (epi-) halohydrin and / or epoxy compounds or derivatives) and / or acylated for example, by agents (ien) with one or more carboxylic acid and / or Carboxylic acid halide and / or carboxylic acid anhydride and / or carboxylic acid ester groups and / or diketene and / or diketene-acetone adduct) and / or reacted with carbonic acid derivatives, that is quasi-acylated (for example, by agents (ies) with one or a plurality of isocyanate and / or urethane and / or carbodiimide and / or uretdione and / or allophanate and / or biuret and / or carbonate groups) and / or sulfamidized.
  • the cationic polyelectrolyte or the cationic polyelectrolyte mixture is preferably used dissolved as ammonium compound, that is, if the amino groups of the cationic polyelectrolyte or cationic Polyelektrolytgemisches present as primary and / or secondary and / or tertiary amino groups, these are at least partially by addition of acid in the Transferred ammonium form.
  • partial alkylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture is effected by introducing substituents having reactive groups through haloalkyl derivatives and / or (epi-) halohydrin and / or epoxy compounds and / or compounds to undergo a Michael analogue addition, such as advantageously acrylates and / or acrylonitrile with amines.
  • the partial acylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture can also be advantageously carried out by introducing substituents with reactive groups by carboxylic acids and / or carboxylic acid halides and / or carboxylic anhydrides and / or carboxylic acid esters and / or diketenes, or a quasi-acylation be realized by isocyanates and / or urethanes and / or carbodiimides and / or uretdiones and / or allophanates and / or biurets and / or carbonates.
  • the cationic polyelectrolytes synthesized synthetically via polymerization and / or polycondensation have molecular weights ⁇ 50,000 D (daltons) and even more advantageously molecular weights ⁇ 10,000 D, and the optimum range of molecular weight for each specific cationic polyelectrolyte must be determined in experiments.
  • the surface-modified glass fibers are advantageously also prepared by using the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges in water, preferably as ammonium compound be in the case of primary and / or secondary and / or tertiary amino groups to the aqueous solution of carboxylic acid (s) and / or mineral acid (s) are added to convert the amino groups in the ammonium form.
  • ammonium compound be in the case of primary and / or secondary and / or tertiary amino groups to the aqueous solution of carboxylic acid (s) and / or mineral acid (s) are added to convert the amino groups in the ammonium form.
  • modified glass fiber surfaces according to the invention as polyelectrolyte complex A, which are at least partially and preferably completely covered with at least a hydrolysis-stable and alkali-resistant cationic polyelectrolyte or a hydrolysis-stable and alkali-resistant polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges, directly after their Production and coating / surface modification and / or reactively reacted later with other materials to form chemically ionic and / or covalent bonds.
  • hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant polyelectrolyte mixture and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges on the glass fiber surface as polyelectrolyte A complex or after further modification with further polyelectrolyte (mixture ) and / or polyelectrolyte complexes reactive and / or activatable groups in the form of functional groups and / or olefinically unsaturated double bonds, which are reacted with functionalities of the other materials to form chemically covalent bonds reactive.
  • the modification according to the invention of the glass fiber surface can advantageously also be realized on commercially produced and sized glass fiber surfaces or plain and silane-free glass fiber surfaces by adding an aqueous solution with a maximum concentration of 5% by weight of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or at least partially covering a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges, using cationic polyelectrolytes or cationic polyelectrolyte mixtures having a molecular weight below 50,000 daltons.
  • cationic agents are understood to mean the cationic polyelectrolytes used and present on the glass surface and / or the cationic polyelectrolyte mixture and / or the polyelectrolyte complex with an excess of cationic charges.
  • Example 54 for the cationic polyelectrolytes polyallylamine, polyethyleneimine (branched), polyamidoamine, cationic copolymerimide (prepared from alternating propene / maleic anhydride copolymer reacted with N, N-dimethylamino-n-propylamine and imidized ) and a 1: 1 mixture of polyethylenimine (branched) and polyallylamine and polyDADMAC depending on the type of polycation (mixture) s, the charge density, the degree of branching and the molecular weight surprisingly complete and very stable coverage of the glass fiber surfaces via pH-dependent Zeta potential measurements detected.
  • the known addition reaction of the amino-group-sensitive fluorescent marker fluorescamine was used in the case of cationic agents with amino groups for the detection. Also a intensive washing with dilute acids or alkalis or refluxing or extraction for several hours in water with dilute acetic acid did not change the analytical statements that the surface modification is in an optimal coverage.
  • the position of the isoelectric point and the course of the zeta potential curves are almost congruent before and after washing or extraction, which proves the stability of this surface modification on the glass fibers.
  • both the position of the isoelectric point and the course of the zeta potential curves in the surface-modified glass fibers of the present invention change.
  • asymmetric polyelectrolyte complex is meant when there is a higher concentration of cationic charge agents as compared to anionic charge agents in the polyelectrolyte complex, thus forming “asymmetric polyelectrolyte complexes” that can change and stabilize by rearrangement.
  • an excessively high concentration of agents with cationic charges would be present in comparison to the anionic glass fiber surface and thus form an asymmetric polyelectrolyte complex as polyelectrolyte complex A.
  • the glass fiber surfaces modified according to the invention can be further modified directly in the glass fiber production process or below.
  • the thus modified glass fibers can be further processed directly after the glass fiber manufacturing process or subsequently to a reinforcing material for textile concrete.
  • Glass fibers can be modified according to the invention directly after the glass fiber production or wound up and stored for example only as glass fiber roving, and then according to the invention modified to a reinforcing material for textile be further processed.
  • the existing surface modification can be further modified by adding hydrolysis-stable and alkali-resistant anionic polyelectrolytes or hydrolysis-stable and alkali-resistant anionic polyelectrolyte mixtures to another polyelectrolyte complex.
  • anionic polyelectrolytes or anionic polyelectrolyte mixtures preferably dissolved in water, for example:
  • (Meth) acrylic acid copolymers which are present without and / or with at least one further functional group other than carboxylic acid which has been introduced via the copolymerization and / or which are at least one further functional group other than carboxylic acid and / or or with at least one olefinically unsaturated double bond which are coupled via a polymer-analogous reaction / modification of the (meth) acrylic acid group, are present, and which are preferably water-soluble, and / or
  • modified itaconic acid (anhydride) (co) polymers which are preferably present in the acid and / or monoester and / or monoamide and / or water-soluble imide form and / or which are present without and / or with residual anhydride groups and / or which are present without and / or with at least one further functional group introduced via the copolymerization, and / or which have at least one further functional group and / or at least one olefinically unsaturated double bond which has a polymer-analogous reaction / Modification of preferably itaconic acid (anhydride) groups are coupled, and which are preferably water-soluble, and / or
  • modified fumaric acid copolymers which are preferably present in the acid and / or monoester and / or monoamide form and / or which are present without and / or with at least one further functional group introduced via the copolymerization and / or or, which are present with at least one further functional group and / or at least one olefinically unsaturated double bond, which are coupled via a polymer-analogous reaction / modification of preferably fumaric acid groups, and which are preferably water-soluble, and / or
  • anionically modified (meth) acrylamide (co) polymers which are present without and / or with at least one further functional group which has been introduced via the copolymerization, and / or which have at least one further functional group and / or with at least one olefinically unsaturated double bond which has a polymer-analogous Implementation / modification of the preferred (meth) Arcylamidoli coupled, are present, and which are preferably water-soluble, and / or
  • Sulfonic acid (co) polymers such as styrenesulfonic acid (co) polymers and / or vinyl sulfonic acid (co) polymers in acid and / or salt form, which react with at least one further reactive functional group for coupling reactions, the have been introduced via the copolymerization, and / or which are coupled with at least one further reactive functional group for coupling reactions and / or at least one olefinically unsaturated double bond for radical coupling reactions which are coupled via a polymer-analogous conversion / modification to sulfonic acid groups, for example via sulfonic acid amide groups, are present, and which are preferably water-soluble, and / or
  • cationic polyelectrolytes or cationic polyelectrolyte mixtures modified prior art prior to application in the glass fiber manufacturing process and having no silane groups and modified with specific functional groups for reaction and / or compatibilization with a matrix material or at least one component of the matrix material / equipped and / or equipped with functions such as for improving slip properties by amidation with fatty acids, has proved to be less effective in terms of attachment and optimal occupation density on the glass fiber surface and the reinforcing effect, since the direct attachment and interaction with the Glass fiber surface, usually superimposed by steric effects, is impaired.
  • the dry, modified glass fibers are reactively reacted as hydrolysis-stable and alkali-resistant polyelectrolyte complex A with amino and / or ammonium groups on the surface in the first stage directly in the pultrusion process.
  • duromer (co) polymers for example: - Epoxy resins or
  • UP resins, vinyl ester resins or SMC resin mixtures wherein the UP, vinyl ester or SMC resin mixture comprises a reactive component having at least one reactive functional group for coupling with amino groups on the polyelectrolyte complex A modified glass fiber surface and having at least one olefinically unsaturated double bond for reaction with the unsaturated matrix component (s) (such as glycidyl methacrylate (GMA) and / or (meth) acrylic anhydride and / or (meth) acryloyl chloride and / or allyl glycidyl ether and / or tetrahydrophthalic anhydride and / or maleic anhydride and / or Itaconic anhydride) was added.
  • unsaturated matrix component such as glycidyl methacrylate (GMA) and / or (meth) acrylic anhydride and / or (meth) acryloyl chloride and / or allyl glycidyl ether
  • anionic polyelectrolyte or the anionic polyelectrolyte mixture which may also be modified with special functional groups and / or olefinically unsaturated double bonds for reaction and / or compatibilization with matrix materials and / or optionally with functions such as for improving the sliding properties, are commercially available, for example as (meth) acrylic acid copolymer derivatives and / or (modified) maleic acid (anhydride) copolymer derivatives and / or (modified) itaconic acid (anhydride) (co) polymer derivatives and / or (modified) fumaric acid Copolymer derivatives and / or styrenesulfonic acid (co) polymer derivatives and / or anionically-treated acrylamide (co) polymer derivatives are widely available.
  • the essence of this invention is that the glass fiber surface without using sizing and / or silane in the first step with a mono (macro) possible molecular layer of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and / or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and / or a hydrolysis-stable and alkali-resistant polyelectrolyte complex is provided with an excess of cationic charges with a layer thickness in the nanometer range, and after the (polyelectrolyte) complex formation on the glass fiber surface a hydrolysis-stable and alkali-resistant polyelectrolyte complex A prepared and coupled by ionic bonds to the glass surface is present, wherein at least one further (Co) polymer is the Polyelektrolytkomplex A at least partially covered and coupled to the polyelectrol
  • hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and / or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures formed on the glass fiber surface form a very stable polyelectrolyte complex A and the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures are no longer conventional Dissolution and / or extraction process can be separated from the glass surface.
  • a partial to almost complete removal of the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and / or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and / or the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges from the glass fiber surface would be conceivable and possible only with a strong anionic polyelectrolyte in that, in an equilibrium reaction in an aqueous medium, the cationic agents from the glass surface, as it were, by the formation of a separate polyelectrolyte complex in the solution, combine with this strong anionic polyelectrolyte and thus "rearrange".
  • a weak cationic compound deposited on the glass surface can be exchanged for stronger cationic agents with, for example, quaternary ammonium groups, if an excess of strong cationic polyelectrolyte or cationic polyelectrolyte mixture is used in the exchange reaction.
  • polyelectrolytes are understood to mean water-soluble compounds of large chain length (polymers) which carry anionic (polyacids) or cationic (polybases), dissociable groups (Wikipedia, keyword polyelectrolytes).
  • Adsorption of such polyelectrolytes on the glass fiber surface occurs by adsorbing dissolved cationic agents onto the oppositely charged anionic glass fiber surface.
  • the adsorption is driven, inter alia, by the electrostatic attraction between the charged monomer units of the polyelectrolytes and oppositely charged dissociated surface groups on the glass fiber surface, for example SiO groups on silica surfaces.
  • the release of counterions or the formation of hydrogen bonds allow adsorption.
  • the conformation of the polyelectrolyte in the dissolved state determines the adsorbed amount of substance.
  • Elongated polyelectrolyte molecules adsorb as thin films (0.2 to 1 nm) on the surface, whereas nucleated polyelectrolyte molecules form thicker layers (1 to 8 nm) (Wikipedia, keyword polyelectrolytes).
  • a stable cohesively bonded surface modification of the glass fibers is achieved with a preferably complete coverage of the glass fiber surface, and stable compounds dissolved in water are used which do not age during application Furthermore, it is not necessary to use sizing mixtures or sizing dispersions, and it is not absolutely necessary to use silanes for coupling to the glass fiber surface, which change chemically over time in water.
  • non-alkali-resistant glass fibers such as the cheaper E glass fibers can be used after the surface modification of the invention and the cohesive coating as a reinforcing material for textile concrete.
  • the production and modification of glass fibers especially as roving (glass fiber bundles) to reinforcing materials for use in textile concrete is carried out in the examples on an E-glass spinning plant on a pilot plant scale for spinning and online surface modification of glass fibers.
  • the plant has finishing stations, which can be used downstream of the multi-stage order immediately after the spinning process, and a Metrorovingwickler.
  • the sump is filled with an aqueous solution of various hydrolysis-stable, preferably unmodified and alkali-resistant cationic polyelectrolytes and / or of various hydrolysis-stable, preferably unmodified and alkali-resistant cationic polyelectrolyte mixtures.
  • various hydrolysis-stable, preferably unmodified and alkali-resistant cationic polyelectrolytes and / or of various hydrolysis-stable, preferably unmodified and alkali-resistant cationic polyelectrolyte mixtures Depending on the take-off speed, filament yarns of 50 to 200 tex can be spun with the machine.
  • Example 1 a Surface sealing with epoxy
  • the dried surface-modified glass roving material-1 is drawn through an impregnating bath with thermosetting epoxy so as to be impregnated with the epoxy resin for surface treatment, the excess adhering epoxy is separated by passing over rubber rollers, and thereafter after forming, this epoxy-treated glass fiber roving material is passed through a heating section , in which the material is partially cross-processed into a cohesive, compact prepreg strand and wound up after a cooling section (prepreg strand material-1).
  • a cohesively, with a thicker epoxy resin layer surface-modified prepreg strand material-1 is further processed in this form as a reinforcing material for textile concrete as follows:
  • the prepreg strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and cross-laid in a heated press on a 2 mm thick HNBR plate, on which a 0.125 mm PTFE peel-off film as a release layer is placed placed at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet.
  • this prepreg reinforcement material is cured for 1 hour at 165 ° C., the partially crosslinked epoxy resin of these strands forms a stable handling compound at the points of intersection during the consolidation process. After cooling, a lattice network is ready as a reinforcing material for use in textile concrete.
  • Example 1 b Surface coating with thermoplastic polyurethane
  • the modified glass fiber roving epoxy resin seal prepreg strand 1 produced in Example 1a is passed through a die in a second stage and coated / wrapped with a melt of thermoplastic polyurethane (TPU). During the coating, in addition to the thermal Curing of the partially cured epoxy resin in the interface between epoxy resin and TPU coupling reactions instead. Under formation of covalent bonds is the
  • TPU with the epoxy resin chemically coupled as cohesive composite before. After a cooling section, the TPU strand material-1 is wound up.
  • This TPU strand material-1 is further processed as reinforcing material for textile concrete as follows:
  • the TPU strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and cross-laid in a heat press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been laid as a release layer placed at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet.
  • this reinforcing material is pressed for 30 minutes at 190 ° C, the strands form a stable for handling at the crossing points by melting the TPU for handling. After cooling, this lattice network is used as reinforcing material in textile concrete.
  • Example 1c Surface coating with maleic anhydride-grafted polypropylene
  • the prepreg strand material-1 prepared in Example 1a is passed through a nozzle in a second stage and coated / enveloped with a melt of maleic anhydride-grafted polypropylene (PP-gMAn).
  • PP-gMAn maleic anhydride-grafted polypropylene
  • the PP-gMAn is present with the epoxy resin as a cohesive, chemical composite. After a cooling section, the PP-gMAn strand material-1 is wound up.
  • This PP-gMAn strand material-1 is further processed as reinforcing material for textile concrete as follows:
  • the PP-gMAn strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been applied as a release layer. placed crosswise at intervals of about 4 cm. Then one will second 0.125 mm PTFE peel sheet also positioned as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 30 minutes at 160 ° C, the strands form at the crossing points by fusing the PP gMAn a sufficiently stable for handling compound. After cooling, this lattice network is used as reinforcing material in textile concrete.
  • Example 1 d Surface sealing with UP resin and coating with PP-gMAn
  • the dried surface-modified glass roving material-1 is pulled through an impregnating bath of UP resin to which 5 mass% of glycidyl methacrylate (GMA) has been added, so as to be impregnated with the UP resin for surface treatment.
  • the excess UP resin is separated by passing over rubber rollers and subsequently, after shaping, this UP resin-treated glass fiber roving material is passed through a heating section in which the material is crosslinked into a cohesive, compact strand and wound up after a cooling section.
  • the strand is passed through a die in which the strand is coated / wrapped with a melt of maleic anhydride-grafted polypropylene (PP-gMAn).
  • PP-gMAn maleic anhydride-grafted polypropylene
  • coupling reactions take place in the interface between the GMA-modified UP resin and the PP-gMAn.
  • Forming covalent bonds, the PP-gMAn with the UP resin surface is a cohesive, chemical composite.
  • the UP-PP-gMAn strand material-1 is wound up.
  • This UP-PP gMAnStrangmaterial-1 is further processed in this form as reinforcing material for textile concrete as follows:
  • the UP-PP-gMAn strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm thick PTFE peel-off film as a release layer was placed, arranged crosswise at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet.
  • this reinforcing material is pressed for 20 minutes at 160 ° C, wherein the strands at the crossing points by fusing the PP gMAn one for the Handling sufficiently stable composite form. After cooling, this lattice network is used as reinforcing material in textile concrete.
  • Example 1 e Surface sealing with PP-gMAn
  • the dried, surface-modified glass roving material-1 is extrusion-coated and enveloped by pultrusion directly with a low-viscosity, maleic anhydride-grafted polypropylene (PP-gMAn) and made into a narrow tape.
  • PP-gMAn low-viscosity, maleic anhydride-grafted polypropylene
  • coupling reactions take place in the interface between the glass fibers of glass roving material-1 and the PP-gMAn.
  • the PP-gMAn is present over the polyelectrolyte complex A with the glass fibers as a cohesive, chemical bond.
  • the material is wound up as a narrow PP-gMAn tape material-1.
  • This PP-gMAn tape material-1 is further processed in this form as a reinforcing material for textile concrete as follows:
  • the PP-gMAn tape material-1 is cut into strands of 0.5 m for a demonstrator test and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been applied as a release layer. placed crosswise at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 15 minutes at 160 ° C, the tapes at the crossing points by melting the PP-gMAn form a sufficiently stable for handling handling. After cooling, this lattice network is used as reinforcing material in textile concrete.
  • Example 1f Surface sealing with PP-gMAn and coating with PP
  • the dried, surface-modified glass roving material-1 is coated by pultrusion directly with a low-viscosity, maleic anhydride grafted polypropylene (PP-gMAn) by infiltration and enveloping (as in Example 1 e).
  • PP-gMAn low-viscosity, maleic anhydride grafted polypropylene
  • infiltration and coating coupling reactions take place in the interface between the glass fibers of glass roving material-1 and the PP-gMAn.
  • Under Formation of covalent bonds is the PP-gMAn on the polyelectrolyte complex A with the glass fibers as cohesive, chemical composite before.
  • this strand is then passed through a nozzle and coated with a viscous PP material, wherein the two polypropylenes merge in the interface.
  • the PP-gMAn-PP strand material-1 is wound up.
  • This PP-gMAn-PPStrangmaterial-1 is further processed in this form as reinforcing material for textile concrete as follows:
  • the PP-gMAn-PP strand material-1 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm thick PTFE peel-off film as a release layer was placed, arranged crosswise at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 30 minutes at 170 ° C, wherein the strands form at the crossing points by fusing the PP material of the outer layer sufficiently stable for handling. After cooling, this lattice network is used as reinforcing material in textile concrete.
  • PolyDADMAC polydiallyldimethylammonium chloride, Aldrich, M w ⁇ 100,000, very low molecular weight
  • the PolyDADMAC as a strong cationic polyelectrolyte possesses only quaternary ammonium groups and otherwise no further olefinically unsaturated double bonds and / or reactive functional groups which are relevant for chemical radical, addition and substitution reactions, direct reactions are not possible.
  • the PolyDADMAC surface-modified glass fiber is treated with an anionic polyelectrolyte having a further functional group other than the anionic group for chemical coupling and / or compatibilization with the matrix material or at least one component of the matrix material, and a polyelectrolyte complex "glass fiber surface / PolyDADMAC / anionic polyelectrolyte "
  • Modification variant via the Polyelektrolytkomplex Struktur is preferably used for polyDADMAC surface-modified glass fibers.
  • the polyDADMAC surface-modified glass fiber roving in a technically analogous apparatus such as the sizing station by rewinding by means of a roller with a 0.5% old propen-maleic acid-N, N-dimethylamino-n-propyl-monoamide Solution (prepared from alt-propene-maleic anhydride by reaction with N, N-dimethylamino-n-propylamine in the ratio of anhydride to primary amino group of 1 to 0.4 in water) to form the polyelectrolyte complex "glass fiber surface / PolyDADMAC / an ionic polyelectrolyte" treated , wound up and dried (Glasrovingmaterial-2).
  • Example 2a Surface sealing with epoxy and coating with PA12
  • the dried, surface-modified glass roving material-2 is drawn through an impregnating bath of thermosetting epoxy so impregnated with the epoxy resin for surface treatment, the excess adhering epoxy is separated by passing over rubber rollers, and thereafter, after molding, this epoxy-treated glass fiber roving material is passed through a heating section , in which the material is partially cross-processed into a cohesive prepreg strand and wound up after a cooling section (prepreg strand material-2).
  • This prepreg strand material-2 is passed through a nozzle in a second stage and coated / encased with a melt of PA12. During the coating, in addition to the thermal curing of the partially cured epoxy resin in the interface between epoxy resin and PA12 coupling reactions take place. Forming covalent bonds, the PA12 is chemically coupled to the epoxy resin as a cohesive bond. After a cooling section, the PA12 strand material 2 is wound up. This PA12 strand material 2 is further processed as reinforcing material for textile concrete as follows:
  • the PA12 strand material-2 is cut into strands of 0.5 m for a demonstrator experiment and placed crosswise in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been laid as a release layer placed at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet.
  • this reinforcing material is pressed for 30 minutes at 190 ° C, the strands form at the crossing points by fusing the PA12 a stable for handling compound. After cooling, this lattice network is used as reinforcing material in textile concrete.
  • Example 2b Surface sealing with UP resin
  • the dried surface-modified glass roving material-2 is pulled through an impregnating bath with UP resin to which 5% by mass of glycidyl methacrylate has been added, so as to be impregnated with the UP resin for surface treatment.
  • the excessively adhering UP resin is separated by scrapers.
  • this UP resin-treated glass fiber roving material is passed through a heating section in which the material is partially cross-linked to form a cohesive, compact strand and wound up after a cooling section (prepreg strand material-3).
  • This prepreg strand material-3 is further processed as reinforcing material for textile concrete as follows:
  • the prepreg strand material-3 is cut into strands of 0.5 m for a demonstrator experiment and cross-laid in a heat press on a 2 mm thick HNBR plate, over which a 0.125 mm PTFE peel-off film has been laid as a release layer placed at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet.
  • this reinforcing material is pressed for 20 minutes at 180 ° C, with the partially crosslinked UP resin of these strands at the crossing points during the consolidation process forms a stable for handling composite.
  • a lattice network is available as reinforcing material for use in textile concrete.
  • the prepreg strand material-3 is passed through a nozzle in a second process step and coated with an ABS melt. During coating, coupling reactions take place in the interface between the partially crosslinked UP resin and the ABS, and the UP resin continues to harden. Forming covalent bonds, the ABS with the UP resin surface is a cohesive, chemical composite. After a cooling section, the ABS-UP resin strand material-2 is wound up.
  • This ABS-UP resin strand material-2 is further processed as a reinforcing material for textile concrete as follows:
  • the ABS-UP resin strand material-2 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate, onto which a 0.125 mm PTFE peel-off film as release layer was placed, arranged crosswise at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet. Under moderate pressure, this reinforcing material is pressed for 15 minutes at 200 ° C, whereby the UP resin of these strands hardens and the strands form a stable for handling by fusing the ABS at the crossing points. After cooling, a lattice network is available as reinforcing material for use in textile concrete.
  • the pH-dependent zeta potential measurements on the glass fibers treated in this way demonstrate the adsorption of PEI / polyallylamine on the surface.
  • Example 3a Sealing with epoxy and coating with PA6
  • the dried, surface-modified glass roving material-3 is pulled through an impregnating bath with thermosetting epoxy and so impregnated with the epoxy resin for surface treatment.
  • the excessively adhering epoxy is separated by passing over rubber rollers and subsequently, after shaping, this epoxy-treated glass fiber roving material is passed through a heating section in which the material is partially cross-linked to a cohesive, compact prepreg strand and wound up after a cooling-down path (prepreg). strand material-3).
  • This prepreg strand material-3 is passed through a nozzle in a second stage and coated / encased with a melt of PA6. During the coating, in addition to the thermal curing of the partially cured epoxy resin in the interface between epoxy resin and PA6 coupling reactions take place. Forming covalent bonds, the PA6 is chemically coupled with the epoxy resin as a cohesive bond. After a cooling section, the PA6 strand material-3 is wound up.
  • This PA6 strand material 3 is further processed as reinforcing material for textile concrete as follows:
  • the PA6 strand material-3 is cut into 0.5 meter strands for a demonstrator experiment and cross-stacked in a heated press on a 2 mm thick HNBR plate, over which a 0.125 mm PTFE peel-off film is placed as a release layer placed at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet.
  • This reinforcing material is pressed under moderate pressure for 10 minutes at 230 ° C., the strands forming a stable bond at the points of intersection by fusion of the PA6. After cooling, this lattice network is used as reinforcing material in textile concrete.
  • Example 3b Epoxy sealing and coating with PE-coAAc ionomer
  • the dried, surface-modified glass roving material-3 is processed into a prepreg strand material-3 (as in Example 3a).
  • This prepreg strand material-3 is passed through a die in a second stage and coated / encased with a melt of PE-coAAc ionomer (polyethylene-co-acrylic acid ionomer, Surlyn, DuPont).
  • PE-coAAc ionomer polyethylene-co-acrylic acid ionomer, Surlyn, DuPont.
  • the coating in addition to the thermal curing of the partially cured epoxy resin, coupling reactions take place in the interface between the epoxy resin and the PE-coAAc ionomer. Forming covalent bonds, the PE-coAAc ionomer is chemically coupled with the epoxy resin as a cohesive bond. After a cooling section, the PE-coAAc strand material-3 is wound up.
  • This PE-coAAc strand material-3 is further processed as reinforcing material for textile concrete as follows:
  • the PE-coAAc-strand material-3 is cut into strands of 0.5 m for a demonstrator experiment and placed in a heatable press on a 2 mm thick HNBR plate on which a 0.125 mm PTFE peel-off film has been applied as a release layer. placed crosswise at intervals of about 4 cm.
  • a second 0.125 mm PTFE peel sheet is also positioned thereon as a release liner and a 2 mm thick vulcanized HNBR sheet.
  • This reinforcing material is pressed under moderate pressure for 15 minutes at 120 ° C., the strands forming a stable bond for handling at the points of intersection by fusion of the PE-coAAc ionomer. After cooling, this lattice network is used as reinforcing material in textile concrete.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Abstract

L'invention concerne les domaines de la chimie et de la construction et porte sur des fibres de verre à surface modifiée pour le renforcement du béton, telles qu'elles peuvent par exemple être utilisées dans les bétons armés de textile (béton textile). Le problème à la base de la présente invention concerne des fibres de verre à surface modifiée pour le renforcement du béton, qui sont au moins protégées essentiellement contre une attaque alcaline par les hydrates de chaux libérés lors de la réaction cimentaire et/ou contre les processus de dissolution et de lessivage ainsi générés. Le problème est résolu par des fibres de verre à surface modifiée pour le renforcement du béton, qui sont recouvertes au moins partiellement par un polyélectrolyte cationique stable à l'hydrolyse et résistant aux alcalis et/ou par un mélange polyélectrolytique cationique stable à l'hydrolyse et résistant aux alcalis et/ou par un complexe polyélectrolytique stable à l'hydrolyse et résistant aux alcalis et qui sont couplées via une formation de complexe (polyélectrolytique), par liaison ionique, à la surface des fibres de verre avec formation du complexe polyélectrolytique A stable à l'hydrolyse et résistant aux alcalis, au moins un autre (co)polymère recouvrant au moins partiellement le complexe polyélectrolytique A et étant couplé au complexe polyélectrolytique A via des liaisons ioniques et/ou covalentes.
EP18733539.3A 2017-06-15 2018-06-14 Fibres de verre à surface modifiée pour le renforcement du béton et procédé pour leur fabrication Withdrawn EP3638717A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017113205.8A DE102017113205A1 (de) 2017-06-15 2017-06-15 Oberflächenmodifizierte Glasfasern zur Betonverstärkung und Verfahren zu ihrer Herstellung
PCT/EP2018/065804 WO2018229186A1 (fr) 2017-06-15 2018-06-14 Fibres de verre à surface modifiée pour le renforcement du béton et procédé pour leur fabrication

Publications (1)

Publication Number Publication Date
EP3638717A1 true EP3638717A1 (fr) 2020-04-22

Family

ID=62712963

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18733539.3A Withdrawn EP3638717A1 (fr) 2017-06-15 2018-06-14 Fibres de verre à surface modifiée pour le renforcement du béton et procédé pour leur fabrication

Country Status (5)

Country Link
US (1) US20200216358A1 (fr)
EP (1) EP3638717A1 (fr)
CN (1) CN110753719A (fr)
DE (1) DE102017113205A1 (fr)
WO (1) WO2018229186A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110698096A (zh) * 2019-11-18 2020-01-17 衡阳县海华水泥有限责任公司 一种玻璃纤维复合水泥及其制备方法
CN114276057B (zh) * 2021-12-24 2023-04-07 深圳市纳路特建材科技有限公司 隔热水泥砂浆及其应用
CN115028412A (zh) * 2022-06-22 2022-09-09 西安科技大学 一种毛细管引导原位封堵水泥基复合材料及其使用方法
CN115286274B (zh) * 2022-08-24 2023-03-28 河北工业大学 一种再生玻璃钢纤维耐碱涂层的制备方法
DE102023203726A1 (de) 2023-04-24 2024-10-24 Sgl Carbon Se Bewehrungseinheit
CN117335017B (zh) * 2023-11-09 2024-06-25 旭派电源有限公司 一种铅酸电池高分子胶体电解质及其制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3367793A (en) * 1964-01-15 1968-02-06 Burlington Industries Inc Coated glass textile and process of making same
US3746738A (en) 1972-03-28 1973-07-17 Union Carbide Corp Silicon containing polyazimides
GB1465059A (en) * 1973-07-03 1977-02-23 Pilkington Brothers Ltd Glass fibres
GB1511270A (en) * 1975-12-17 1978-05-17 Owens Corning Fiberglass Corp Method of making a glass-fibre-reinforced cementitious composition
US4241136A (en) * 1979-03-05 1980-12-23 Owens-Corning Fiberglas Corporation Glass fiber size composition and process
US4935301A (en) * 1988-12-16 1990-06-19 Exxon Research And Engineering Compnay Coated glass fiber composites
DD300535A5 (de) * 1990-06-28 1992-06-17 Akad Wissenschaften Ddr Tensidhaltiges schlichtemittel zur behandlung von fasern
DE102005048190A1 (de) * 2005-09-30 2007-04-05 Leibniz-Institut Für Polymerforschung Dresden E.V. Beschichtung in verstärkten Verbundwerkstoffen
EP2530216A1 (fr) 2011-05-30 2012-12-05 Groz-Beckert KG Corps de construction préfabriqué en béton textile
EP2828313B1 (fr) * 2012-03-20 2016-05-18 3B-Fibreglass SPRL Composition d'encollage en deux parties destinée au revêtement de fibres de verre et composite renforcé par de telles fibres de verre
DE102015100438B3 (de) 2015-01-13 2016-03-24 Technische Universität Dresden Herstellung von Fertigteilen aus Textilbeton

Also Published As

Publication number Publication date
CN110753719A (zh) 2020-02-04
DE102017113205A1 (de) 2018-12-20
WO2018229186A1 (fr) 2018-12-20
US20200216358A1 (en) 2020-07-09

Similar Documents

Publication Publication Date Title
EP3638717A1 (fr) Fibres de verre à surface modifiée pour le renforcement du béton et procédé pour leur fabrication
AU759430B2 (en) Sizing for glass fibers having low nonionic and cationic lubricant content
US20080143010A1 (en) Chemical coating composition for glass fibers for improved fiber dispersion
WO2007024683A1 (fr) Mat formé en voie humide présentant de meilleures résistances à la rupture par traction à chaud dans des conditions humides
DE102006062733B4 (de) R- E- und ECR-Glasfasern mit wässriger Schlichte und deren Verwendung
DE69224821T2 (de) Schlichtzusammensetzungen fur glas und damit beschichtete glasfasern
WO2009086152A2 (fr) Dispersion variable de fibres de verre à fils coupés utilisées en voie humide dans un mat à fils coupés
DE68926908T2 (de) Verfahren zum Kleben von aromatischen Polyamidfasern an Gummimischungen
WO2015057763A1 (fr) Mat non-tissé souple
RU2600369C2 (ru) Стекловолоконные пряди и содержащие их армированные изделия
BR0210465B1 (pt) fio de vidro revestido de uma composição de encolamento, composição de encolamento, e, placa compósita.
WO2018229187A1 (fr) Surfaces modifiées de fibres de verre, exemptes d'ensimage et exemptes de silane, matériaux composites produits à partir de celles-ci et procédé pour la production des surfaces modifiées en fibres de verre
US11970801B2 (en) Corrosion-resistant non-woven for pipe liner pultrusion applications
EP2048122A1 (fr) Analyse aqueuse destinée à la fabrication de produits en fibres de verre
CN101421320B (zh) 用于混凝土的制剂
DE102008064662B4 (de) Fasern aus R-, E-, ECR- oder S-Glas und Verwendung der Fasern
DE102006035565B4 (de) Wässrige Schlichte zur Behandlung von R-,E- und ECR-Glasfasern und deren Verwendung
DE2056540A1 (de) Schlichte fur Glasfasern
DE2553839A1 (de) Beschlichtete glasfasern
DE2426654A1 (de) Beschlichtete glasfasern
DE202008015660U1 (de) Wässrige Textilschlichte zur Behandlung von R-, E-, ECR- und S-Glasfasern
DE1494860C (de) Verfahren zum Überziehen von mineralischen Fasern
JP2003301334A (ja) ゴム補強用炭素繊維束、ゴム補強用コードおよび繊維強化ゴム材料
DD283597A5 (de) Verbundwerkstoff mit alkalisch reagierender matrix und einer glaskomponente sowie deren verwendng
DE2010950A1 (en) Elastomeric produce reinforced with glass

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20191212

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
18D Application deemed to be withdrawn

Effective date: 20201120