DE2156686A1 - Glass fibres partly surface modified - by adsorption of org molecules/ions as mono layer, used in filter fleeces and epoxy - Google Patents

Abstract

The fibres have 20-75% of their surface modified by adsorption of a monolayer of org. molecules and/or ions which are practically statistically distributed. The molecule(ion) is bound to the fibres by a siloxane bridge, and tri/tetra valent heavy metal ion complex, a hydrogen bond with a polymer e.g. OVA or polyacrylamide, dipole exchange with silicone oils or ionogenic exchange with polycations e.g. polyethyleneimine or polyanions e.g., polyacrylic acid. The fibres are modified by contact with a medium contg. 10-5-10-9 mole/l. of the molecule (ion). They are used in gas filters for chromatographic columns, liquid-aerosols esp. for tobacco smoke filters and are inrocporated in epoxy resin laminates.

Description

G r e n z f LÄ c h e n m o d <1 i f i z i e r t e G 1 a 5 f a s e r n The invention relates to interface modified glass fibers, in particular Microglass fibers, in which 20 to 75 of the surface due to immobile adsorption with approximately statistically distributed organic molecules or molecular ions covered and the fiber surface, compared to the surface of native glass fibers, an altered interfacial activity compared to liquid and gaseous The purpose of the invention is to determine the surface properties of microglass fibers to be changed in such a way that it is used, for example, as a filter material or as a reinforcement element in glass fiber reinforced plastics are optimally adapted to a specific task.

It has long been known that treatment with organic substances to a change in the mechanical and surface chemical properties of Fiber optic leads. This subheading includes sizing and flattening processes, adhesion promoters, Binders and all kinds of impregnations. In all of the balls, the fiberglass is preserved a closed one, usually even a multiple molecular coating.

Such multi-coated glass fibers are already in many patents has been proposed as filter material 1) In such synthetic resin-bonded glass fiber filters the content of organic matter is usually greater than o.5 Gewo. SMIl'H 2) describes an image medium at. which is a mat made of uncoated glass fibers Is enclosed on both sides by synthetic resin-bonded fiberglass mats, according to JACKSON 3) filter fleeces are made from a mixture of cellulose and glass fibers. PINTER 4) recommends using glass fiber fleeces e.g. with @ 5% alcoholic solutions of Polyoxyethylene sorbitan monooleate (Tween 80) or polyoxyethylene sorbitan monolaureate (Tween 20) to soak and then to air dry.

Hartl: 11 Interface-modified glass fibers "11/15/71 for improvement the adhesive forces between glass fibers and casting resins are determined according to current regulations zoBo 1oo 2 fibers coated with 15 to 1 g of an adhesion promoter a closed multiple molecular layer is formed, which forms the fiber surface isolated from the surrounding medium This also applies to silicone adhesion promoters5) e.g. for chloro-chromium-methacrylate and other products.

It is state of the art that glass fibers are either completely uncoated (native or desized) or their surface with a relatively thick To completely cover the layer of organic material0 There is no procedure yet became known in the case of glass fibers, the surface of which is only partially covered with organic Molecules is covered, manufactured or used0 The invention resides in the Task underlying the surface of glass fibers in statistically distributed areas break down, part of which is hydrophilic, the rest of which is organophilic interfacial properties has, and both the absolute and the relative dimensions of the sub-areas to vary through targeted measures, through the choice of appropriate organic ones Molecules or molecular ions should also optimize the respectively required Interface properties can be achieved 0 This object is achieved according to the invention solved that organic molecules or molecular ions that help to form strong bonds are able to be attached to glass surfaces, in the medium which the glass fibers to be modified surrounds, are contained in extremely low concentration, and that the dispersion medium, which can be liquid or gaseous, relative to the fibers in rapid motion is located. After the modification, the dispersion medium is separated from the glass fibers. (Embodiments 1 to 14) The modification according to the invention provides glass fibers, where 20 to 75 fo the surface with organic molecules or molecular ions are covered. (Occupancy density 20 to 75 go) Depending on the dimensions and conformations of the molecules, this corresponds to attached amounts of 35 to 550 Micrograms r) ro m2 fiber surface. Fibers 1.5 micrometers in diameter (special @rtl: "Interface modified Glass fibers "11/15/71 specific surface around 1 m2g-1) therefore have a content of organic matter from 30 to 500 ppm.

Table 1 contains values for E-glass fibers with a diameter of 1.5 μm in the addition of trimethylsilyl, dimethyl octadecylsilyl and trioctadecylsilyl groups have been obtained at different occupancy densities.

Tab.1 Amount of trialkylsilyl groups in µg per m2 fiber surface different occupancy densities.

Org. Amount accumulated per m2 fiber surface in µg group with an occupancy density of 20% 60% 65% 70% (C1B3) 3Si- 35 - 13o C18H37 (CH3) 2Si- 80 - 250 - (C18H37) 3Si- 180 550 - -The attachment of organic molecules or molecular ions causes the inherently hydrophilic glass fiber surface to be randomly distributed Areas, the extent of which can be between 25 and 1,000 max. 1o,000 Å2, are organophilic will. While the hydrophilic properties are directly on the unoccupied fiber surface originate from the organophilic properties, depending on the size of the organic molecule, more or less far in the direction of the elongated fiber radius. This spatial separation of hydrophilic and organophilic areas in the direction of the fiber radius, which is around 15 Å with stearylammonium ions, for example the thickness of a 5 to 7-fold layer of water molecules, has the consequence that organophilic and hydrophilic interrelationships on the one hand largely undisturbed next to each other on the other hand because of the distances that are limited to molecular dimensions can be linked cooperatively with one another.

The advantages that can be achieved with the invention are, in particular, that random filter made of microglass fibers modified according to the invention in view on performance, flow resistance, Hartl: "Interface Modified Glass fibers "11/15/71 capacity and selectivity can be varied within wide limits can because the filter properties both by the area density and the distribution pattern as well as by the type of molecules or molecular ions bound to the fiber surface can be influenced.

Especially when filtering liquid aerosols, their particle phase consists of organophilic and hydrophilic components, such filters are the hitherto superior to known systems when combined with extremely high filter capacity good selectivity and low pressure drop across the filter is required. Therefore appear the glass fibers according to the invention are suitable for the production of exhaust gas filters. Their use for tobacco smoke filters should be particularly promising, as here the selectivity of the filtration plays an important role9 further with the invention achievable advantages lie in the possibility of the mechanical properties of e.g. epoxy resin-glass fiber laminates by using glass fibers according to the invention instead of glass fibers conventionally coated for this application to improve. There is no need to consider the hydrolytic effects to a considerable extent the glass fiber-epoxy resin interface must be accepted.

Finally, there is an essential advantage of the modification according to the invention to see that they can be achieved with simple, rapid processes without toxicity or corrosion problems can be run e Landes et al. USPs 2,694,630 et al. 2 758 o26 Mauthner DBP 1 o94 176 BP 757 841 Smith et al. USP 2,797,163 Hungerford et al. USP 2 9o6 660 OBryant USP 3 o19 854 Best USP 3 023 839 Parmele USP 3,039 908 2) Smith USP 2 971 907 3) Jackson USP 3 o12 929 4) Pinter USP 3 412 737 5) Pamphlets from Wacker-Chemie GmbH: SM 706.457, SM 708.458, SM 6711.439, SM 647.419, SM 37.406 SM 37.407 SM 687.444 Hartl: "Interface-modified glass fibers" 11/15/71 Working Examples 1. Addition of vinyl-triacetoxysilane from the gas phase 1 g of native micro-glass fiber (Johns Manville 475 / 1o8, 1.5 µm base diameter) Spread loosely in a 2 liter flask and store at 60 ° C for 10 minutes exposed to a vinyltriacetoxysilane partial pressure of o.o1 Torr, the modified in this way Basers have an occupancy density of 5o%.

2. Addition of trimethylchlorosilane from the gas phase 1 g of glass microfiber (Johns Manville, E-Glass, 1.3 am fiber diameter, native to be medium Fiber length of 5 mm -cut and in a vortex chamber of 25 liters through a stream of air is circulated about twice per second or 1 mg of trimethylchlorosilane sprayed into the vortex chamber at room temperature in the course of 60 seconds Quantities of hydrogen chloride are then captured by soda lime. Occupancy density 45%.

3. Addition of tetrakosamethyl-undecasiloxane from the gas phase Ein Air flow is in a heated to 50 ° C column with gaseous tetrakosamethyl-undecasiloxane (Silicone oil) saturated and mixed with additional air to such an extent that the partial pressure of the silicone oil o.oo1 Torr is 1 g of native E-glass fibers (see 2!) 250 ° C in the course of 10 minutes with 25o liters of this silicone oil-containing air. Occupancy density 30%.

This embodiment shows that a modification according to the invention also directly after the fiber drawing process.

can be made, but this would be a closed one Luftumwälzung 'recommend, since a quantitative conversion of the silicone oil is not achieved will.

4. Addition of polyvinyl alcohol from the aerosol phase 1 g glass fiber are, as described under 2), but at 70 ° C in the vortex chamber with a finely divided aerosol sprayed from 1 ml of a chloroform solution of o.1 mg of polyvinyl alcohol (Molecular weight approx. 17,000) is generated. Do the check-in Hartl: "Interface Modified Glass fibers "15.11.71 hen the vortex chamber is kept in operation for another 3 minutes and then the chloroform vapor is drawn off. The occupancy density is 35%.

5. Addition of triphenyl-methoxysilane from the aerosol phase 1 g Glass fibers (see 2!) Are exposed to an air stream at 200 ° C in which an aerosol a solution of 0.2 mg triphenylmethoxysilane in 1 ml trichlorethylene in the course of 60 seconds is injected. After the solvent vapors have been driven off, the Treatment completed. Occupancy density 55%.

6. Addition of 2-amino-2'-trimethoxysilyl-diethylamine from aqueous Solution to be 500 g of native fiber (Johns Manville 475/108, 1.5 µm fiber diameter) suspended in 75 liters of water and subjected to a cyclic crushing process. Cycle time approx. 10 seconds. In the course of 60 seconds, 1000 ml of a solution containing 13 mg of 2-amino-2'-trimethoxysiliyl-diethylamine per liter was added. The cycle is then maintained for a further minute. The fibers can then filtered off and getrock @ et at room temperature or elevated temperature or after appropriate dilution of the suspension by known methods to be processed into a fleece. The occupancy density is 40%. Colloidal and - to a lesser extent - ionic constituents of water can lead to lead to a reduction in occupancy density.

7. Addition of stearyl-methyl-dichlorosilane from non-aqueous solution 1 g of native glass fiber (Johns Manville 475/108, 1.5 μm fiber diameter) are added Cut 5 mm mean fiber length and suspended in 3 liters of carbon tetrachloride. With vigorous stirring, 100 ml of carbon tetrachloride, which o.2 mg Containing stearyl-methyl-diehlorsilane, added.

The fibers are filtered off after 10 minutes and air-dried. Occupancy density 25% 0.

Hartl: "Interface-Modified Glass Fibers" 11/15/71 8. Addition of stearato-chromium (III) chloride from aqueous solution 500 g of fibers are produced analogously to 6) treated with 40 mg stearato-chromium (III) chloride. Occupancy density 20%.

9. Addition of polyvinylpyridinium-N-hexyl chloride from aqueous colloidal solution 550 g of fibers are treated analogously to 6) with a solution which contains 33 rag polyvinylpyridinium-N-hexyl chloride (molecular weight approx. 1,000,000) in colloidal dispersion per liter . as 13eleg icht the result is a value of 30%.

10. Addition of octadecamethyl-octasiloxane from aqueous emulsion 1 g of native fibers (Johns Manville, E-Glas, 1.3 µm fiber diameter) are shortened and suspended in 5 liters of water by vigorous stirring. Then 50 ml of an o.oo1% emulsion of Octadecamet'lyl-Octasiloxan (silicone oil), the was produced by means of ultrasound without stabilization, slowly added dropwise. 3 minutes after the addition is complete, the fibers are filtered off and allowed to air or dried at 120 ° C. In both cases the occupancy density was 60%.

11 @. Addition of polyethyleneimine from aqueous solution 1 g native Glass fiber (Johns Manville 475/108, 1.5 µm fiber diameter) are on a medium Fiber length of 5 mm cut and dispersed in 5 liters of water by vigorous stirring. 100 ml of an aqueous solution of 0.4 mg polyethyleneimine (molecular weight approx. 100 000) are added dropwise over the course of 2 minutes. The pH value of the solution increases from 6.3 to 8.5. After the addition was complete, the dispersion medium was drawn off. Occupancy density 30%.

12. Addition of polyacrylic acid amide from aqueous solution analogous to 11) the modification with 0.5 mg polyacrylic acid amide (molecular weight 3 to 4 Million). The pH dropped from 6.3 to 4.8. The occupancy density revealed up to 25%.

Hartl: "Interface-modified glass fibers" 11/15/71 13th attachment of polyvinylpyridinium-N-dodecyl chloride from aqueous suspensions 500 g fibers are analogous to 6) with 100 ml of a suspension homogenized by ultrasound, which contains 60 mg of polyvinylpyridinium-N-dodecyl chloride, added. Occupancy density turned out to be 30%.

14. Addition of triphenyl-ethoxysilane from aqueous suspension 500 g fibers are treated analogously to 13), with 100 ml of a homogenized suspension of 15 mg triphenyl-ethoxysilane can be used. Occupancy density 20%.

Basically, the occupancy densities are increased by changing the Ratio of the amount of fiber to the amount of organic molecules or molecular ions, or to vary their concentration.

Hartl: "Interface-modified glass fibers" 11/15/71 - @ - Examples of use 1. Selective adsorption from gaseous media filter columns with the invention modified glass fibers are filled, show depending on the type of modification a selective retention against various vaporized hydrocarbon compounds Tab. 2 Ret ### tion behavior of glass fiber filters towards various hydrocarbon compounds Fiberglass +) Occupancy Higher Lower modified dense retention compared to with. % Stearates 40 n-alkanes branched and chromium (III) - prim. Ring-shaped alkanols Chloride alkanes triphenyl 55 aromatics alkanes methoxysilane polyvinyl 50 aromatics branched and pyridinium n-alkanes circular N-dodecyl alkanes chloride 2-arnino-2-'tri- 60 lower carboxylic aliphatic methoxysilyl acids, phenols and aromatic Diethylamine Amines +) Johns Manville, E-Glass, 1.3 @m fiber diameter 2. Adsorption from solutions Only then can pronounced adsorption effects be achieved in solutions if between the solvent and the dissolved substance sufficiently large constitutional and functional differences exist. E.g. from a 0.01 frigen solution of stearyl alcohol in methanol per gram of stearyl methyl dichlorosilane modified Glass fiber (Johns Manville, E-glass, or 5 µm fiber diameter, occupancy density 65%) up to 3 g of stearyl alcohol can be bound.

3. Adsorption from emulsions Compared to emulsions from non-polar organic Compounds in water show glass fibers modified with tristearyl chlorosilane (Johns Manville 475/108, 1.3 µm fiber diameter, 40 laying density) a high specific adsorption. You can- Hartl: "Interface Modified Glass fibers "15.11.71 e.g. from o.o1 show emulsions of heating oil in water up to bind to 1 g of 01 per gram of fiber. This effectiveness also exists against oil films on water. The fibers can be quickly removed after use, e.g. by washing them out with trichlorethylene be regenerated.

40 Filtration of cigarette smoke The filter performance of glass fiber fleece discs, which were installed transversely / to the smoke flow in place of the usual filter, was determined using the TPM (total particulate matter) method.

Gave. 3 Specific separation performance and nicotine content in the filtered Smoke after filtering through glass fiber fleece-glass fiber +) Occupancy TPM specific Nicotine content modified dense waste in the filtered with power smoke% mg / cig. % ++) wt.% +++) water (comparative 12.1 360 5.6 sample) N- (3-oxypropyl; - aminopropyl- 50 1o.1 460 5.5 diethoxysilane methacryloxypropyl 55 10.7 450 5.1 trimethoxysilane Polyvinylpyridinium 30 10.6 460 5.2 N-dodecyl chloride glycidoxy propyl methyl 45 10.4 400 5.7 Tetrasiloxane +) Johns Manville 475/108, 1.5 µm fiber diameter ++) Weight of condensate / weight of filter in% +++) based on the TPM value Table 3 shows that the separation efficiency of filter fleeces from fibers modified according to the invention is approx. 25 ß higher than Hartl: "Interface Modified Glass fibers "11/15/71 - @ - for comparable nonwovens made from untreated fibers Selectivity towards the deposition of nicotine can be determined with the modification also influence: With organic molecules or molecular ions, the olefinic or have aromatic groups, the nicotine content is significantly reduced found in filtered smoke.

Similar results are obtained when the fiberglass filter is not as fleece discs, but as spherical or ellipsoidal tangles in the smoke stream lie. However, the specific separation capacities are substantial lower values, 5. Reinforcement of epoxy resin Heat-desized glass fabric 181 was in an aqueous medium with various amounts of methacryl-oxypropyl-trimethoxysilane modified. In addition, another tissue sample was taken using conventional methods treated with the same adhesion promoter.

The variously modified fabrics were hand-laid Test specimen made of 12 layers of glass fabric and epoxy resin and these after Hardness tested according to DIN 53 452.

Tab. 4 Flexural strength of glass fiber reinforced epoxy resin test specimens according to DIN 53 452 silicone content covering flexural strength residual strength in the fabric density dry 100 hours cooked weight%% kpcm-2 kpcm-2% approx. 4. 10-4 approx. 20 4 100 2 300 56 approx. 6. 1 10-4 approx. 35 4 600 2 400 52 approx. 7. 10-4 approx. 50 5 200 2 800 54 approx. 9. 10-4 approx. 60 4 900 2 800 57 .approx. 12. 10-4 approx. 75 4 850 2 9oo 60 (multiple 0.5 4 700 3 100 66 molecular layers)

Claims (1)

G R e n z f l a c h e n m o d i f i z i e r t e glass fibers Patent claims 1. . Interface-modified glass fibers, in particular micro-glass fibers, thereby characterized in that 20 to 75% of their surface area is due to immobile adsorption a monomolecular layer of approximately statistically distributed organic molecules and / or molecular ions is covered and the fiber surface thereby, in comparison to the surface of native glass fibers, compared to a changed interface activity having solid, liquid and gaseous substances, 2. glass fibers according to claim 1, characterized in that the attached molecules or molecular ions 20 to 50% of the fiber surface cover0 3. Glass fibers according to claims 1 and 2, thereby characterized in that the attached molecules or molecular ions have relatively strong Bonds are attached to the fiber surface and thus their primary distribution pattern is stabilized. 40 glass fibers according to claim 3, characterized in that the bond takes place via siloxane bridges. 50 glass fibers according to claim 3, characterized in that the bond takes place through complex formation with trivalent or tetravalent heavy metal ions, 6 Glass fibers according to claim 3, characterized in that the bond is multiple Hydrogen bonds between the fiber surface and a polymer such as polyvinyl alcohol or polyacrylic acid amide. 7. Glass fibers according to claim 3, characterized in that the bond occurs through dipole interactions, as is the case with silicone oils on polar surfaces. 8. Glass fibers according to claim 3, characterized in that the bond through multiple ionogenic interactions between the fiber surface and organic ones Polycations, such as polyethyleneimine, or polyanions, such as polyacrylic acid, took place 9. Glass fibers according to claim 3, characterized in that the attached molecules or molecular ions due to their rest constitutional and / or functional Properties to be intense and / or selective interactions with the modified Fibers surrounding medium are capable of 0 10. Glass fibers according to claim 9, characterized in that that the moles contain bad or molecular ions contain aliphatic groups, 11 OGlassfans: ern according to claim 9, characterized in that the molecules or molecular ions are aromatic and / or olefinic groups contained 12. Glass fibers according to claims 1o and 11, characterized in that the organic groups are, for example, amino, hydroxy or Have carboxy functions, 13. Cast resin laminates made of glass fibers according to the claims 1 to 12, characterized in that they, compared to laminates from conventional treated glass fibers, achieve a higher strength, 14.Method of manufacture of glass fibers according to claims 1 to 122, characterized in that the molecules or molecular ions as a function of their molecular weight in the modification Concentrations between 10 5 and 10-9 Mo] per liter in the one surrounding the fibers Have medium. 15. The method according to claim 14, characterized in that the the medium surrounding the fibers is gaseous 0 16 The method according to claim 14, characterized in that characterized in that the medium surrounding the fibers is an aerosol 17. Method according to claims 15 and 16, characterized in that the modification is both can be carried out at lower as well as at higher temperatures up to 300 ° C. 18. The method according to claim 17, characterized in that the modification can be carried out directly after the fiberglass drawing process. 19. The method according to claim 14, characterized in that the the The medium surrounding the fibers is a true or colloidal solution0 20 Claim 14, characterized in that the medium surrounding the bases is an emulsion ist0 21 0 Method according to Claim 14, characterized in that the fibers surrounding medium is a suspension. 22e filter column made of glass fibers according to claims 1 to 12, characterized characterized in that they differ in chromatographic processes with respect to mixtures of substances behaves selectively. 23. Filter ball made of glass fibers according to claims 1 to 12, characterized characterized in that it is used for the filtration of tobacco smoke, in particular cigarette smoke, suitable is0 24. Nonwovens made of glass fibers according to claims 1 to 12, characterized in that that they, made without a binder, as a low-drag filter, in particular for liquid aerosols. 25. Nonwovens according to claim 24, characterized in that they are adaptable for installation in cigarette mouthpieces and achieve high filtration performance in the separation of the particle phase from cigarette smoke, 26 filters according to claims 23 and 25, characterized in that their efficiency and / or their Selectivity with respect to multi-substance aerosols, in particular tobacco smoke, can be optimized