GLASS FIBER SURFACES WHICH ARE MODIFIED WITHOUT SIZING MATERIAL AND SILANE, COMPOSITE MATERIALS PRODUCED THEREFROM, AND METHOD FOR PRODUCING THE MODIFIED GLASS FIBER SURFACES

Abstract

The invention pertains to the fields of chemistry and mechanical engineering and relates to glass fiber surfaces which are modified without sizing material and silane, which glass fiber surfaces can be further processed into and used as composite materials, for example as reinforcing fiber materials for plastics, and to a method for producing the modified glass fiber surfaces. The object of the present invention is to provide glass fiber surfaces modified without sizing materials and silane, which glass fiber surfaces exhibit improved properties overall and for a further processing into composite materials, and furthermore to provide a simple and cost-effective method for producing glass fiber surfaces modified in such a manner. The object is attained with glass fiber surfaces modified without sizing material and silane, which glass fiber surfaces are at least partially covered at least with a hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte and/or hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture and/or with a hydrolysis-stable and/or solvolysis-stable polyelectrolyte complex and coupled to the glass fiber surface via a (polyelectrolyte) complex formation process by means of ionic bonding, with the polyelectrolyte complex A thereby being formed.

Claims

1. Glass fiber surfaces modified without sizing material and silane, which glass fiber surfaces are at least partially covered at least with a hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte and/or hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture and/or a hydrolysis-stable and/or solvolysis-stable polyelectrolyte complex and coupled to the glass fiber surface via a (polyelectrolyte) complex formation process by means of ionic bonding, thereby forming the polyelectrolyte complex A.

2. The glass fiber surfaces modified without sizing material and silane according to claim 1 in which a hydrolysis-stable and/or solvolysis-stable polyelectrolyte complex A is present which has been created by a (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and/or solvolysis-stable cationic polyelectrolytes; and/or by a (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixtures; and/or by a (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and/or solvolysis-stable polyelectrolyte complexes having an excess of cationic charges, which polyelectrolyte complexes have been produced before being applied to the glass fiber surface.

3. The glass fiber surfaces modified without sizing material and silane according to claim 1 in which the hydrolysis-stable and/or solvolysis-stable polyelectrolyte complex A covers the glass fiber surface completely or essentially completely.

4. The glass fiber surfaces modified without sizing material and silane according to claim 1 in which the following are present as hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte or hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture: poly(diallyldimethylammonium chloride) (polyDADMAC) and/or copolymers; and/or polyallylamine and/or copolymers; and/or polyvinylamine and/or copolymers; and/or polyvinylpyridine and/or copolymers; and/or polyethyleneimine (linear and/or branched) and/or copolymers; and/or chitosan; and/or poly(amide-amine) and/or copolymers; and/or cationically modified poly(meth)acrylate(s) and/or copolymers; and/or cationically modified poly(math)acrylamide(s) with amino groups, and/or copolymers; and/or cationically modified maleimide copolymer(s), produced from maleic acid (anhydride) copolymer(s) and (N,N-dialkylaminoalkylene)amine(s), wherein alternating maleic acid (anhydride) copolymers are preferably used; and/or cationically modified itaconic imide (co)polymer(s), produced from itaconic acid (anhydride) (co)polymer(s) and (N,N-dialkylaminoalkylene)amine(s); and/or cationic starch derivatives and/or cellulose derivatives.

5. The glass fiber surfaces modified without sizing material and silane according to claim 1 in which the following are present as functionalities on the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte or hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture: unmodified primary and/or secondary and/or tertiary amino groups that do not have substituents on the amine nitrogen atom with an additional reactive and/or activatable functional group and/or olefinically unsaturated double bond, and/or quaternary ammonium groups which do not have on the nitrogen atom substituents with an additional reactive and/or activatable functional group and/or olefinically unsaturated double bond, and/or have amino groups and/or quaternary ammonium groups which are at least partially chemically modified on the nitrogen atom via alkylation reactions, with at least one additional reactive and/or activatable functional group and/or at least one olefinically unsaturated double bond, and/or have amino groups and/or quaternary ammonium groups and amide groups which are chemically modified via acylation reactions of amino groups to amide, with at least one additional reactive and/or activatable functional group and/or at least one olefinically unsaturated double bond.

6. The glass fiber surfaces modified without sizing material and silane according to claim 1 in which at least one anionic polyelectrolyte or one anionic polyelectrolyte mixture without and/or with at least one additional reactive and/or activatable functional group different from the anionic group and/or with at least one olefinically unsaturated double bond are present as functionalities on the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte or hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture attached to the glass fiber surface.

7. The glass fiber surfaces modified without sizing material and silane according to claim 6 in which the following are present as anionic polyelectrolyte or anionic polyelectrolyte mixture: (a) (meth)acrylic acid copolymers which are present without and/or with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of the (meth)acrylic acid group, and which are preferably water-soluble, and/or (b) 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 additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of maleic acid (anhydride) groups, and which are preferably water-soluble, and/or (c) 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 additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of itaconic acid (anhydride) groups, and which are preferably water-soluble, and/or (d) 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 additional reactive and/or activatable functional group that was introduced via the copolymerization, and or which are present with at least one additional reactive and/or activatable functional group and/or at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of fumaric acid groups, and which are preferably water-soluble, and/or (e) anionically modified (meth)acrylamide (co)polymers which are present without and/or with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of the (meth)acrylamide group, and which are preferably water-soluble, and/or (f) sulfonic acid (co)polymers, such as for example styrenesulfonic acid (co)polymers and/or vinylsulfonic acid (co)polymers in acid and/or salt form, which are present with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of sulfonic acid groups, such as via sulfonic acid amide groups for example, and which are preferably water-soluble, and/or (g) (co)polymers with phosphonic acid groups and/or phosphonate groups, which are for example present such that they are bonded as aminomethylphosphonic acid and/or aminomethylphosphonate and/or amidomethylphosphonic acid and/or amidomethylphosphonate, and/or which are present with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous (co)polymer reaction/modification, and which are preferably water-soluble.

8. The glass fiber surfaces modified without sizing material and silane according to claim 1 in which the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolytes or the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture have a molecular weight under 50,000 dalton, preferably in the range between 400 and 10,000 dalton.

9. Composite materials with glass fibers having glass fiber surfaces modified without sizing material and silane, in which composite materials hydrolysis-stable and/or solvolysis-stable polyelectrolyte complexes A and/or B, which are present in an at least partially covering manner on glass fiber surfaces without sizing material and silane and which comprise functional groups and/or olefinically unsaturated double bonds, are present such that they are coupled via a chemically covalent bond with additional materials after a reaction with functional groups and/or olefinically unsaturated double bonds.

10. The composite materials according to claim 9 in which at least one at least difunctional and/or difunctionalized low-molecular-weight and/or oligomeric and/or polymeric agent with functional groups and/or olefinically unsaturated double bonds are present as additional materials.

11. The composite materials according to claim 9 in which thermoplastics and/or thermosets and/or elastomers are present as additional materials as matrix materials for glass fibers.

12. The composite materials according to claim 9 in which amino groups, preferably primary and/or secondary amino groups, and/or quaternary ammonium groups are present as functionalities of the adsorbed hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte complex.

13. A method for producing glass fiber surfaces modified without sizing material and silane, in which method a hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte and/or a hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture and/or a hydrolysis-stable and/or solvolysis-stable polyelectrolyte complex with an excess of cationic charges is applied from an aqueous solution at a concentration of maximally 5 wt % to the glass fiber surfaces in an at least partially covering manner during or after the production of glass fibers, wherein hydrolysis-stable and/or solvolysis-stable cationic polyelectrolytes and/or hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixtures with a molecular weight under 50,000 dalton and/or a hydrolysis-stable and/or solvolysis-stable polyelectrolyte complex with an excess of cationic charges are used.

14. The method according to claim 13 in which polyelectrolytes which are not subsequently alkylated and/or acylated and/or sulfamidated after production are used as hydrolysis-stable and/or solvolysis-stable cationic polyelectrolytes, or polyelectrolyte mixtures that are not subsequently alkylated and/or acylated and/or sulfamidated after production are used as hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixtures.

15. The method according to claim 13 in which the following are used as hydrolysis-stable and/or solvolysis-stable unmodified cationic polyelectrolyte, as a pure substance or substances or in a mixture, preferably dissolved in water: poly(diallyldimethylammonium chloride) (polyDADMAC) and/or copolymers; and/or polyallylamine and/or copolymers; and/or polyvinylamine and/or copolymers; and/or polyvinylpyridine and/or copolymers; and/or polyethyleneimine (linear and/or branched) and/or copolymers; and/or chitosan; and/or poly(amide-amine) and/or copolymers; and/or cationically modified poly(meth)acrylate(s) and/or copolymers; and/or cationically modified poly(meth)acrylamide(s) with amino groups, and/or copolymers; and/or cationically modified maleimide copolymer(s), produced from maleic acid (anhydride) copolymer(s) and, for example, (N,N-dialkylaminoalkylene)amine(s), wherein alternating maleic acid (anhydride) copolymers are preferably used; and/or cationically modified itaconic imide (co)polymer(s), produced from itaconic acid (anhydride) (co)polymer(s) and, for example, (N,N-dialkylaminoalkylene)amine(s); and/or cationic starch derivatives and/or cellulose derivatives.

16. The method according to claim 13 in which hydrolysis-stable and/or solvolysis-stable cationic polyelectrolytes and/or hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixtures and/or hydrolysis-stable and/or solvolysis-stable polyelectrolyte complexes with an excess of cationic charges are used at a concentration of maximally 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 additional sizing material or sizing material components and/or silanes.

17. The method according to claim 16 in which hydrolysis-stable and/or solvolysis-stable cationic polyelectrolytes which are not subsequently alkylated and/or acylated and/or sulfamidated after production and/or hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixtures that are not subsequently alkylated and/or acylated and/or sulfamidated after production are used at a concentration of <2 wt %, and particularly preferably at <0.8 wt %.

18. The method according to claim 13 in which hydrolysis-stable and/or solvolysis-stable cationic polyelectrolytes and/or hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixtures with a molecular weight under 50,000 dalton, preferably in the range between 400 and 10,000 dalton, are used.

19. The method according to claim 13 in which a modified hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte and/or a hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture that is partially alkylated and/or acylated and/or reacted with carboxylic acid derivatives and/or sulfamidated in a subsequent reaction following production, and is thus equipped with a substituent having reactive and/or activatable groups for a coupling reaction, is then, having the reactive and/or activatable groups of the covalently coupled substituent, reacted with additional materials to form a composite material via at least one functional group and/or via at least one olefinically unsaturated double bond without crosslinking of the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolytes or of the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture.

20. The method according to claim 19 in which the partial alkylation of the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte or of the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture, with substituents having reactive groups thereby being introduced, is achieved through haloalkyl derivatives and/or (epi)halohydrin compounds and/or epoxy compounds and/or compounds which enter into a Michael-analogous addition, advantageously such as acrylates and/or acrylonitrile with amines.

21. The method according to claim 19 in which the partial acylation of the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte or of the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture, with substituents having reactive groups thereby being introduced, is achieved through carboxylic acids and/or carboxylic acid halides and/or carboxylic acid anhydrides and/or carboxylic acid esters and/or diketenes, or in which a quasi-acylation is achieved through isocyanates and/or urethanes and/or carbodiimides and/or uretdiones and/or allophanates and/or biurets and/or carbonates.

22. The method according to claim 13 in which the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolytes and/or the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture and/or the hydrolysis-stable and/or solvolysis-stable polyelectrolyte complexes with an excess of cationic charges are used such that they are dissolved in water, preferably as an ammonium compound, wherein in the case of primary and/or secondary and/or tertiary amino groups carboxylic acid(s) and/or mineral acid(s) are added to the aqueous solution to convert the amino groups into the ammonium form.

23. The method according to claim 13 in which modified glass fiber surfaces that are at least partially, and preferably completely, covered at least with a hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte or a hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture and/or a hydrolysis-stable and/or solvolysis-stable polyelectrolyte complex with an excess of cationic or anionic charges are, directly following the production and coating/surface modification thereof and/or at a later point, reacted with additional materials, with chemically covalent bonds thereby being formed.

24. The method according to claim 23 in which the modified glass fiber surfaces are wound and/or intermediately stored as roving and are subsequently reacted with additional materials, with chemically covalent bonds thereby being formed.

25. The method according to claim 23 or 21 in which the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte or the hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture and/or the hydrolysis-stable and/or solvolysis-stable polyelectrolyte complex with an excess of cationic or anionic charges comprises reactive groups in the form of functional groups and/or olefinically unsaturated double bonds that are reacted with functionalities of the additional materials, with chemically covalent bonds thereby being formed.

26. The method according to claim 13 in which an aqueous solution with a concentration of maximally 5 wt % of a hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte and/or of a hydrolysis-stable and/or solvolysis-stable cationic polyelectrolyte mixture and/or of a hydrolysis-stable and/or solvolysis-stable polyelectrolyte complex with an excess of cationic charges is applied in an at least partially covering manner to commercially produced and sized glass fiber surfaces or to glass fiber surfaces without sizing material and silane, wherein cationic polyelectrolytes or cationic polyelectrolyte mixtures with a molecular weight under 50,000 dalton are used.

Description

EXAMPLE 1

[0236] In the E-glass silk spinning system, glass fibers with 100 tex are spun and are surface-modified and wound in the sizing station, which is filled with an aqueous 0.5% PEI solution as cationic polyelectrolyte (PEI=polyethyleneimine, Aldrich, M.sub.n=10,000).

[0237] The pH-dependent zetapotential measurements on the glass fibers treated in such a manner verify the adsorption of PEI in the polyelectrolyte complex A with the glass fiber surface.

[0238] The detection of coupled amino groups at the surfaces and verification of the uniform coverage of the glass fibers was conducted using the fluorescamine method.

[0239] The surface-modified glass fibers comprise the polyelectrolyte complex A that was formed from the glass fiber surface and PEI.

EXAMPLE 1A: COUPLING WITH EPOXY COMPOUNDS

[0240] A bundle of glass fiber segments (length of 20 mm) was treated with 3,5-dibromophenyl glycidyl ether in ethanol. After the washing, the sample showed in the EDX analyses a uniformly thick coverage with bromine at the glass fiber surface.

[0241] The treatment with the 3,5-dibromophenyl glycidyl ether verifies the reactivity of the glass fiber surface modified with PEI with respect to epoxy resins and verifies the uniform coverage.

EXAMPLE 1B: COUPLING WITH ISOCYANATE AND ISOCYANATE DERIVATIVES

[0242] Analogously, a bundle of glass fiber segments (length of 20 mm) was dried and treated with 2,4-dibromophenyl isocyanate in ether. After the washing with acetone, the sample showed in the EDX analyses a uniformly thick coverage with bromine at the glass fiber surface.

[0243] The treatment with the 2,4-dibromophenyl isocyanate verifies the reactivity of the glass fiber surface modified with PEI with respect to isocyanate compounds, which verifies that these glass fiber products can be used for the reinforcement of PUR and TPU.

EXAMPLE 1C: COUPLING WITH EPOXY RESIN

[0244] In accordance with the method for examining the fiber/matrix adhesion (fiber pull-out method), a glass fiber was embedded in epoxy resin and the pull-out force was determined. With the glass fibers surface-modified with PEI, it was possible to determine a 40% on-average increase in the pull-out force compared to commercially sized glass fibers.

[0245] The embedding furthermore verifies the good bonding and coupling of the PEI surface-modified glass fibers with epoxy resin, and verifies that these glass fiber products can be used for the reinforcement of epoxy resins.

EXAMPLE 1D: COUPLING WITH OLEFINICALLY UNSATURATED MONOMERS

[0246] 5 g of glass fiber segments approx. 20 mm long were treated on a fit with 20 mL of a 0.1% glycidyl methacrylate (GMA)/ethanol solution and the solution was suctioned away. The glass fiber segments were rinsed with ethanol three times and dried. The glass fibers treated in such a manner were degassed and rendered oxygen-free in a 250 mL three-neck flask by means of vacuum application and high-purity nitrogen flushing. Then, a prepared polymerization solution (composed of 100 mL pure toluene distilled under nitrogen, 5 mL destabilized styrene and 50 mg AIBN (azobis(2-methylpropionitrile)) was added under high-purity nitrogen and was reacted with the glass fibers for 3 hours at 50 C. while being stirred. The solution is suctioned away, and the glass fibers are extracted three times with toluene under reflux and subsequently dried in a vacuum. In the ATR spectrum, a non-extractable, chemically coupled polystyrene was detected on the glass fibers, whereby it is verified that, after a GMA treatment with UP resins, these PEI surface-modified glass fibers can be used in SMC production, for example.

[0247] Additional trials have shown that this pretreatment is not necessary if corresponding agents, such as for example GMA and/or allyl glycidyl ether and/or (meth)acrylic anhydride and/or (meth)acrylic chloride, are added to the polymerization system/polymerization solution or the UP resin, which agents on the one hand react with the PEI on the glass fiber surface and on the other hand are capable of a radical coupling reaction/copolymerization.

EXAMPLE 1E: GALVANIZATION OF A PEI-MODIFIED GLASS FIBER SURFACE

[0248] 5 g of glass fiber segments surface-modified with PEI and approx. 20 mm long are stirred for 15 minutes in 100 mL of an aqueous nucleating agent solution temperature-controlled to 50 C. (composed of 1 g/L PdCl.sub.2 and 20 g/L HCl) and suctioned. Palladium nuclei/noble metal nuclei are then produced by a reduction of the palladium ions in a formaldehyde solution. A nickel conductive layer is subsequently applied via chemically reductive deposition to the surface activated in such a manner, which verifies that PEI surface-modified glass fibers can be electrochemically coated with metal at the surface.

EXAMPLE 1F: GALVANIZATION OF A GLASS FIBER SURFACE MODIFIED WITH POLYELECTROLYTE COMPLEX B

[0249] As in Example 1e, palladium nuclei/noble metal nuclei are produced on 5 g of glass fiber segments surface-modified with PEI and approx. 20 mm long. After the rinsing, these glass fibers are then treated with a 0.1% propene-alt-maleic acid n-butylmonoamide solution (produced from propene-alt-maleic anhydride via reaction with n-butylamine in water) for the formation of a polyelectrolyte complex B at the surface. The glass fibers are suctioned and rinsed and the nickel conductive layer is applied via chemically reductive deposition to the glass fiber surfaces activated in such a manner, which verifies that surface-modified glass fibers can be electrochemically coated with metal at the surface.

EXAMPLE 2

[0250] As in Example 1, glass fibers with 100 tex are spun in the E-glass silk spinning system and are surface-modified and wound in the sizing station, which is filled with an aqueous 0.5% polyDADMAC solution as a cationic polyelectrolyte (polyDADMAC=poly(diallyldimethylammonium chloride), Aldrich, M.sub.W<100,000).

[0251] The pH-dependent zetapotential measurements on the glass fibers treated in such a manner verify the adsorption of polyDADMAC onto the surface.

[0252] The surface-modified glass fibers comprise the polyelectrolyte complex A that was formed from the glass fiber surface and polyDADMAC.

[0253] Since polyDADMAC as a strong cationic polyelectrolyte the has only quaternary ammonium groups and otherwise no additional olefinically unsaturated double bonds and/or reactive functional groups that are relevant for chemical radical reactions, addition reactions and substitution reactions, direct reactions are not possible. In this case, for further modification, the glass fiber surface-modified with polyDADMAC is treated with an anionic polyelectrolyte which has an additional functional group, which is different from the anionic group, for the chemical coupling and/or compatibilization with the matrix material or at least one component of the matrix material, and a polyelectrolyte complex B (glass fiber surface/polycation/polyanion) is formed. This modification variant via the polyelectrolyte complex formation process is used for the glass fibers surface-modified with polyDADMAC.

EXAMPLE 2A: COUPLING WITH OLEFINICALLY UNSATURATED MONOMERS

[0254] The glass fiber surface-modified with polyDADMAC is treated in a separate step downstream of the production process with a 0.3% propene-alt-maleic acid n-allylmonoamide solution as an anionic polyelectrolyte (produced from propene-alt-maleic anhydride via reaction with n-allylamine in water at a 1 to 0.4 ratio of maleic anhydride group to allyl amine) for the formation of a polyelectrolyte complex B.

[0255] Glass fiber segments modified in such a manner and approx. 20 mm long were rinsed with ethanol three times and dried. 10 g of these glass fibers were degassed and rendered oxygen-free in a 250 mL three-neck flask by means of vacuum application and high-purity nitrogen flushing. Then, a prepared polymerization solution (composed of 100 mL pure toluene distilled under high-purity nitrogen, 5 mL destabilized styrene and 50 mg AIBN (azobis(2-methylpropionitrile)) was added under nitrogen and was reacted with the glass fibers for 5 hours at 50 C. while being stirred. The solution is suctioned away, and the glass fibers are extracted three times with toluene under reflux and subsequently dried in a vacuum. In the ATR spectrum, a chemically coupled polystyrene not extractable from the glass fibers was detected, whereby it is verified that surface-modified glass fibers of this type can be used with UP resins in SMC production, for example.

EXAMPLE 2B: COUPLING WITH HOT-CURING EPOXY RESIN

[0256] Analogously to Example 2a, the glass fiber surface-modified with polyDADMAC is treated with a 0.2% propene-alt-maleic acid monoethyl ester solution as anionic polyelectrolyte (produced from propene-alt-maleic anhydride via reaction in ethanol under reflux, precipitated in water, decanted and once again dissolved in water with NaOH being added) for the formation of a polyelectrolyte complex B.

[0257] 5 g of surface-modified glass fiber segments were stirred into 20 mL of a mixture of hot-curing epoxy resin (epoxy resin for FR-4 production) and briefly heated to 160 C. so that the resin continued to stay liquid. After the cooling, this glass fiber/resin mixture was treated with MEK (methyl ethyl ketone), and the glass fibers were passed through a frit and washed with hot MEK. The glass fibers treated in such a manner were dried and examined by means of ATR. It was possible to detect coupled epoxy resin residues on the glass fiber surface, which verifies that a coupling of the surface-modified glass fibers with hot-curing epoxy resin took place, and that these glass fiber products can be used for the reinforcement of hot-curing epoxy resins.

EXAMPLE 2C: COUPLING WITH COLD-CURING EPOXY RESIN

[0258] Analogously to Example 2a, the glass fiber surface-modified with polyDADMAC is treated with a 0.5% propene-alt-maleic acid N,N-dimethylamino-n-propylmonoamide solution as an anionic polyelectrolyte (produced from propene-alt-maleic anhydride via reaction with N,N-dimethylamino-n-propylamine in water) for the formation of a polyelectrolyte complex B.

[0259] 5 g of surface-modified glass fiber segments were stirred in 20 mL of a mixture of MEK (methyl ethyl ketone) and bisphenol A diglycidyl ether (MEK/epoxy resin=1/1), and this was stirred for 15 minutes at 50 C. The glass fiber/resin mixture was diluted with MEK, and the glass fibers were passed through a frit and washed with hot MEK. The glass fibers treated in such a manner were dried and examined by means of ATR. Coupled epoxy resin residues were detected on the glass fiber surface, which verifies that a coupling of these surface-modified glass fibers with epoxy resin took place, and that these glass fiber products can be used for the reinforcement of cold-curing epoxy resins.

EXAMPLE 2D: GALVANIZATION OF A GLASS FIBER SURFACE MODIFIED WITH POLYELECTROLYTE COMPLEX B

[0260] Palladium nuclei/noble metal nuclei are produced by immersion and reduction on 10 g of glass fiber segments surface-modified with polyDADMAC and approx. 20 mm long. These glass fibers are treated with a 0.1% propene-alt-maleic acid-n-butylmonoamide solution as an ionic polyelectrolyte (produced from propene-alt-maleic anhydride via reaction with N-butylamine in water) for the formation of a polyelectrolyte complex B at the surface. The glass fibers are suctioned and rinsed and the nickel conductive layer is applied via chemically reductive deposition to the glass fiber surfaces activated in such a manner, which verifies that surface-modified glass fibers can be electrochemically coated with metal at the surface.

EXAMPLE 3

[0261] Analogously to Example 1, in the E-glass silk spinning system glass fibers with 150 tex are spun, and are surface-modified and wound in the sizing station, which is filled with an aqueous 0.8% PEI/polyallylamine solution as a cationic polyelectrolyte (PEI=polyethyleneimine, Aldrich, M.sub.n=10,000, polyallylamine, Aldrich, M.sub.w15,000; PEI/polyallylamine=2/1).

[0262] The pH-dependent zetapotential measurements on the glass fibers treated in such a manner verify the adsorption of PEI/polyallylamine in the polyelectrolyte complex A with the glass fiber surface.

[0263] The detection of coupled amino groups at the surfaces and verification of the uniform coverage of the glass fibers was conducted using the fluorescamine method.

[0264] The surface-modified glass fibers comprise the polyelectrolyte complex A that was formed from the glass fiber surface and the cationic PEI/polyallylamine polyelectrolyte mixture.

EXAMPLE 3A: COUPLING WITH EPOXY RESIN

[0265] In accordance with the method for examining the fiber/matrix adhesion (fiber pull-out method), a glass fiber was embedded in epoxy resin and the pull-out force was determined. With the glass fibers surface-modified with PEI/polyallylamine, it was possible to determine a 30% on-average increase in the pull-out force compared to commercially sized glass fibers.

[0266] The embedding verifies the good bonding and coupling of the surface-modified glass fibers with epoxy resins, and verifies that these glass fiber products can be used for the reinforcement of epoxy resins.

EXAMPLE 3B: COUPLING WITH ISOCYANATE AND ISOCYANATE DERIVATIVES

[0267] Analogously, a bundle of dried glass fiber segments (length of 20 mm) was treated with 2,4-dibromophenyl isocyanate in ether. After the washing with acetone, the sample showed in the EDX analyses a uniform coverage of the glass fiber surface with bromine.

[0268] In addition to the uniform coverage, the treatment with the 2,4-dibromophenyl isocyanate furthermore verifies the reactivity of the glass fiber surface with respect to isocyanate compounds, which verifies that the glass fiber products surface-modified in such a manner can be used for the reinforcement of PUR and TPU.

EXAMPLE 3C: COUPLING WITH OLEFINICALLY UNSATURATED MONOMERS

[0269] 5 g of glass fiber segments approx. 20 mm long were degassed and rendered oxygen-free in a 250 mL three-neck flask by means of vacuum application and high-purity nitrogen flushing. Then, a prepared polymerization solution (composed of 100 mL pure toluene distilled under high-purity nitrogen, 5 mL destabilized styrene, 0.2 mL GMA (glycidyl methacrylate) and 50 mg AIBN (azobis(2-methylpropionitrile)) were added under nitrogen atmosphere and this was reacted with the glass fibers for 3 hours at 50 C. while being stirred. The solution is suctioned away, and the glass fibers were extracted three times with toluene under reflux and subsequently vacuum dried. In the ATR spectrum, a non-extractable, chemically coupled polystyrene was detected on the glass fibers, whereby it is verified that these PEI/polyallylamine surface-modified glass fibers couple with the GMA in the polymerization system and the glass fibers that are GMA-modified in situ copolymerize with styrene; that is, according to the remarks in Example 1d the in situ modification can also be used with UP resins in SMC production, for example.

EXAMPLE 4

[0270] From a commercial glass fiber roving with 100 tex, 10 g of glass fiber segments with a length of 20 mm are cut off, placed in a 100 mL Erlenmeyer flask and treated for 30 minutes with 50 mL of an aqueous 1.0% PEI solution (PEI=polyethyleneimine, Aldrich, M.sub.n=10,000) while being stirred with a magnetic stirrer. The aqueous PEI solution is than decanted, the Erlenmeyer flask is filled with 50 mL distilled water, and these glass fibers are suctioned by means of a frit and washed three times with water and twice with methanol and dried.

[0271] The pH-dependent zetapotential measurements on the glass fibers treated in such a manner verify the adsorption of PEI with the glass fiber surface to form the polyelectrolyte complex A in comparison to the untreated starting material (glass fiber roving).

[0272] The detection of coupled amino groups at the surfaces of the glass fibers was conducted using the fluorescamine method.

[0273] The surface-modified glass fibers comprise the polyelectrolyte complex A that was formed from the glass fiber material and PEI.

EXAMPLE 4A: COUPLING WITH EPOXY RESIN

[0274] Individual glass fiber segments were treated with 3,5-dibromophenyl glycidyl ether in ethanol. After the washing with ethanol, the sample showed in the EDX analyses a uniform coverage of the glass fiber surface with bromine.

[0275] This experiment furthermore verifies the reactivity of this post-treated glass fiber surface with respect to epoxy compounds, that is, epoxy resins.

EXAMPLE 4B: COUPLING WITH ISOCYANATE AND ISOCYANATE DERIVATIVES

[0276] Analogously, dried glass fiber segments (length of 20 mm) were treated with 2,4-dibromophenyl isocyanate in ether. After the washing with acetone, the sample showed in the EDX analyses a uniform coverage of the glass fiber surface with bromine.

EXAMPLE 4C: COUPLING WITH OLEFINICALLY UNSATURATED MONOMERS

[0277] 5 g of glass fiber segments post-treated with PEI solution and approx. 20 mm long were degassed and rendered oxygen-free in a 250 mL three-neck flask by means of vacuum application and high-purity nitrogen flushing. Then, a prepared polymerization solution (composed of 100 mL pure toluene distilled under nitrogen, 5 mL destabilized styrene, 0.2 mL GMA (glycidyl methacrylate) and 50 mg AIBN (azobis(2-methylpropionitrile)) was added under high-purity nitrogen and reacted with the glass fibers for 3 hours at 50 C. while being stirred. The solution is suctioned away, and the glass fibers are extracted three times with toluene under reflux and subsequently dried in a vacuum. In the ATR spectrum, a non-extractable, chemically coupled polystyrene was detected on the glass fibers, whereby it is verified that these post-treated, surface-modified glass fibers reactively couple with GMA and copolymerize in the polymerization system, that is, that commercial glass fibers post-treated in such a manner can also be used in SMC production, for example.