Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
  • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
  • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2938—Coating on discrete and individual rods, strands or filaments
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
  • Y10T428/2969—Polyamide, polyimide or polyester
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31616—Next to polyester [e.g., alkyd]
  • Y10T428/3162—Cross-linked polyester [e.g., glycerol maleate-styrene, etc.]

Definitions

• the invention relates to a size for carbon fibers and glass fibers based on an aqueous dispersion of an epoxy resin and an emulsifier.
• the invention relates to a sizing agent which has the processing properties - fiber strand cohesion, bundling, spreadability, resistance to fluff and lint formation, fiber smoothness and softness, abrasion resistance and easy and non-destructive unwindability of the carbon or glass fiber fiber strands usually stored on bobbins - as well as the physical properties of the composite material containing the treated fibers improved.
• CFRP carbon fiber reinforced plastics
• the matrices of which are reactive resins such as epoxy resins, bismaleimide resins, unsaturated polyester resins or cyanate resins, are preferably used for the purposes mentioned.
• Carbon fibers consist of several hundred to one hundred thousand individual filaments with a diameter of 5 to 20 ⁇ m, a tensile strength of 1000 to 7000 MPa and an elastic modulus of 200 to 700 GPa.
• Carbon fibers are usually produced by exposing a suitable polymer fiber made of polyacrylonitrile, pitch or rayon to changing controlled conditions of temperature and atmosphere.
• carbon fibers can be produced by stabilizing PAN threads or fabrics in an oxidative atmosphere at 200 to 300 ° C and subsequent carbonization in an inert atmosphere above 600 ° C.
• Such methods are state of the art and are described, for example, in H. H coordinatorler, "Reinforced plastics in the aerospace industry", Verlag W. Kohlhammer, Stuttgart, 1986.
• the carbon fibers are subjected to an oxidative surface treatment and then provided with a suitable sizing agent.
• Glass fibers are cooled by spraying with water after exiting the spinning plate and then provided with the sizing agent by passing them on a rotating roller before the individual filaments are combined into so-called rovings, wound up into a spinning cake and then dried in an oven.
• the size should ensure uniformly good wetting of the fibers by the matrix material during the composite material manufacturing process.
• the size in its entirety must be chemically compatible with the respective matrix material in order to enable high-quality and durable composite materials. Even if the composite is exposed to constantly changing conditions of temperature and moisture, no delamination processes that are the result of incompatibilities and water absorption should occur.
• epoxy resins as the basis of many sizing agents, in particular for carbon fibers, is probably due on the one hand to the fact that epoxy resins are generally used as matrices for the production of CFRP, so sizing / matrix incompatibilities are hardly to be feared, on the other hand to the Relatively high and therefore unspecific chemical reactivity of the oxirane ring towards a variety of functional groups, which means that other than epoxy resins can also be used as a matrix in CFRP.
• sizing agents for carbon fibers can be divided into two classes, the solution and the emulsion type.
• the polymer usually a resin
• emulsion type is a water-dispersed resin supported by dispersing aids, hereinafter referred to as "emulsifiers”.
• emulsifiers water-dispersed resin supported by dispersing aids
• the emulsion-type size is applied to the carbon fibers in such a way that the fiber bundle is continuously passed through the aqueous dispersion, diluted to 1 to 10% by weight solids, and the fiber is dried immediately afterwards and wound onto spools for transport and storage or directly further processing is supplied; the polymer content on the fiber treated in this way is then about 0.5 to 7% by weight.
• highly diluted aqueous dispersions of highly viscous, non-self-emulsifying epoxy resins tend to have low emulsion stability - large particle diameters, chemically incompatible and / or low molecular weight emulsifiers are the cause.
• the need for emulsifier increases, i.e. proportional to the increase in surface area of dispersed particles.
• the finest possible dispersion is a basic requirement so that the particles can easily penetrate into the interior of the bundle.
• a block copolymer of polyethylene oxide and polypropylene oxide of the schematic formula is said to be the emulsifier be used.
• epoxy resin sizes based on such emulsifiers have considerable disadvantages: on the one hand, the film-forming properties of these dispersions are only moderate, on the other hand, laminates made of epoxy resin as a matrix and carbon fibers treated with these size dispersions show increased water absorption, which causes delamination and thus low mechanical strength this composite leads under hot and humid conditions.
• this emulsifier has 80% by weight terminating hydrophilic aliphatic groups, namely polyethylene oxide, and 20% by weight hydrophobic aliphatic groups, namely polypropylene oxide; the dried size proves to be extremely hygroscopic. Added to this is the unsatisfactory chemical compatibility of these aliphatic emulsifiers with the hydrophobic, predominantly aromatic nature of the epoxy resins.
• Such dispersions do not have sufficient storage stability and have too little film-forming properties when diluted strongly; moreover, they are unable to sufficiently and evenly emulsify very fine epoxy resin particles.
• the object of the present invention is to provide a sizing agent for the treatment of carbon fibers and glass fibers, which is free from organic solvents and therefore harmless with regard to toxicity and flammability, which improves the handling and processing properties of the fiber strands and also preserves them in the long term, which is very good has chemical compatibility with epoxy resin matrices over a wide range of temperature and moisture influences and thus ultimately leads to improved mechanical properties of the composite materials, produced from an epoxy resin as a matrix and sized carbon or glass fibers.
• This object is achieved according to the invention by means of a size comprising an epoxy resin and 5 to 50% by weight, based on the epoxy resin, of a polyester of the general formula A1-B-A2-B-A3-H, where the symbols have the following meaning: A1 is the remainder of a mono alcohol, B is the rest of a dicarboxylic acid, A2 is the remainder of a diol, A3 is the remainder of a polyether diol, and the polyester has a molecular weight between 5,000 and 50,000.
• the polyesters preferably have a molecular weight between 10,000 and 25,000.
• the weight ratio (A1 + B + A2 + Z + Y): X is between 80:20 and 40:60.
• polyesters are good emulsifiers which have a molecular weight between 5000 and 50,000 and consist of a hydrophobic molecular part M and a hydrophilic polyethylene oxide molecular part XH, the weight ratio M: X being between 80:20 and 40:60, preferably between 70:30 and 50:50.
• a polyester with a M: X ratio of greater than 80:20 no longer has a sufficient emulsifying effect for the epoxy resin; with an M: X ratio of less than 40:60, the size proves to be too hygroscopic.
• one equivalent of the monoalcohol A1-H is preferably first reacted with about one equivalent of the dicarboxylic acid H-B-H or its anhydride by a conventional condensation reaction to give the half-ester A1-B-H.
• this half-ester is condensed with about one equivalent of the diol H-A2-H or preferably the corresponding diepoxide until the acid number has dropped below 1 mg KOH / g.
• another equivalent of dicarboxylic acid H-B-H or the corresponding anhydride and about 1 equivalent of the polyether diol H-A3-H are added and condensed until the acid number has dropped below 1 mg KOH / g.
• Preferred mono alcohol A 1 H are octylphenoxypolyethoxyethanol with a molecular weight of about 640, and nonylphenoxypolyethoxyethanol with a molecular weight of about 615.
• Preferred dicarboxylic acids H-B-H are tetrahydrophthalic acid, adipic acid, fumaric acid and maleic acid, but it is also suitable, for example, itaconic acid, succinic acid, ortho- and metaphthalic acid, terephthalic acid and, if appropriate, their anhydrides.
• the diols H-A2-H are preferably used in the form of the corresponding diepoxides.
• Preferred diepoxides are the diglycidyl ether of bisphenol A and F with an epoxy equivalent weight of about 100 to 1000.
• diols H-A3-H are preferred: a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer with a molecular weight of about 14,000, and a corresponding block copolymer with the molecular weight of about 9,000; also polyethylene oxide with a molecular weight of about 4000.
• the main constituent of the carbon fiber or glass fiber size according to the invention is an epoxy resin.
• the usual glycidyl ethers of mono- or polyfunctional, preferably aromatic alcohols with epoxy equivalent weights of 100 to 1500 g / eq are suitable.
• Diglycidyl ethers of bisphenol A and F are preferred.
• 100 parts by weight of epoxy resin are preferably combined with 5 to 40, in particular 8 to 30 parts by weight of the emulsifier, heated and homogenized with stirring until a clear melt is formed. Then, with vigorous stirring, add as much in portions Water is added until a homogeneous oil-in-water emulsion forms, which can then be diluted as desired.
• the finished dispersion preferably has a solids concentration of 1 to 10% by weight.
• This size is characterized by the following properties: very fine-particle dispersion with high storage stability, good film-forming properties and excellent emulsion stability, including the highly diluted dispersion.
• the size according to the invention to the carbon fibers, these are drawn through the size dispersion and then dried in a drying shaft with air at 150 ° C.
• the fiber should then contain 0.3 to 10% by weight, preferably 0.5 to 2% by weight, of the size.
• the application of the size to glass fibers has already been defined at the beginning.
• Examples I to IX describe the preparation of polyesters, emulsifiers according to the invention being produced according to Example I-V.
• Examples X to XXIII describe the preparation of epoxy resin dispersions.
• Emulsifiers according to Examples I to V according to the invention were used in X to XIV and XVI to XXI.
• Examples XV and XX to XXV are not according to the invention; emulsifiers according to Examples VI to IX or the known, not inventive emulsifiers Pluronic L 31 and Pluronic F 108 from BASF Corp. used.
• Example II The procedure is as in Example I, but instead of the octylphenoxypolyethoxyethanol used there, 1239 parts of nonylphenoxypolyethoxyethanol with a molecular weight of approximately 615 g / mol (Ethylan BCP from Lankro Chemicals Ltd.) are now used.
• Example II The procedure is as in Example I, but instead of the polyethylene oxide-polypropylene oxide block copolymer used there, 16,600 parts of an analogously structured compound having a molecular weight determined by vapor pressure osmometry of 9700 g / mol (Pluronic F68 from BASF Corp.) are used.
• Example II The procedure is as in Example I, but instead of the polyethylene oxide-polypropylene oxide block copolymer used there, 2200 parts of an analogously structured compound having a molecular weight determined by vapor pressure osmometry of 1070 g / mol (Pluronic L31 from BASF Corp.) are now used.
• Example II The procedure is as in Example I, but instead of the polyethylene oxide-polypropylene oxide block copolymer used there, 12000 parts of a polyethylene oxide with a molecular weight determined by vapor pressure osmometry of 6200 g / mol (Pluriol E6000 from BASF AG) are now used.
• Example II The procedure is as in Example I, but instead of the polyethylene oxide-polypropylene oxide block copolymer used there, 800 parts of a polyethylene oxide with a molecular weight determined by vapor pressure osmometry of 410 g / mol (Pluriol E400 from BASF AG) are now used.
• Example II The procedure is as in Example I, but instead of the polyethylene oxide-polypropylene oxide block copolymer used there, 400 parts of a polyethylene oxide with a molecular weight determined by vapor pressure osmometry of 210 g / mol (Pluriol E200 from BASF AG) are now used.
• Example X The procedure is as in Example X, but the melted resin preparation to be dispersed is composed of 100 parts of a diglycidyl ether of bisphenol A with an epoxide equivalent weight of 190 g / eq (Epikote 828 from Shell), 170 parts of a diglycidyl ether of bisphenol A with an epoxide equivalent weight of 475 g / eq (Shell's Epikote 1001) and 265 parts of a diglycidyl ether of bisphenol A with an epoxy equivalent weight of 860 g / eq (Shell's Epikote 1004) and 95 parts of the emulsifier prepared according to Example I.
• a diglycidyl ether of bisphenol A with an epoxide equivalent weight of 190 g / eq Epikote 828 from Shell
• Example X The procedure is as in Example X, the resin melt preparation to be dispersed being composed of 72 parts of a diglycidyl ether of bisphenol A with an epoxide equivalent weight of 190 g / eq (Epikote 828 from Shell), 72 parts of a diglycidyl ether of bisphenol A with an epoxide equivalent weight of 475 g / eq (Shell's Epikote 1001), 388 parts of a bisphenol A diglycidyl ether with an epoxy equivalent dish of 870 g / eq (Shell's Epikote 1004) and 182 parts of the emulsifier described in Example I.
• the initial temperature of the resin melt preparation at the start of the dispersion is 75 ° C.
• Example X The procedure is as in Example X, but instead of the emulsifier used there are now 95 parts of a polyethylene oxide-polypropylene oxide block copolymer of the approximate formula with a molecular weight determined by vapor pressure osmometry of 1070 g / mol (Pluronic L31 from BASF Corp.).
• the addition of further water leads to the irreversible breakdown of the dispersion (emulsion splitting) in order to set the desired final concentration.
• the polymer is deposited in the form of a slime.
• Example X The procedure is as in Example X, but now 95 parts of the emulsifier still produced in Example III are used instead of the emulsifier used there.
• the dispersion obtained is slightly yellowish.
• Properties of the resin melt preparation before dispersing * Epoxy equivalent weight (potentiometric): 390 g / eq * Brookfield viscosity at 60 ° C: 25,000 mPas * Glass transition temperature (DSC): -3 ° C
• Properties of the aqueous dispersion obtained * Solids content: * Particle size distribution (laser light scattering): 90% ⁇ 2.4 ⁇ m 50% ⁇ 1.2 ⁇ m 10% ⁇ 0.6 ⁇ m * Gravimetric stability of the dispersion diluted with deionized water to 3% FG after 24 h: 98.8% * Tyndall effect: very strong * Appearance of a 15 ⁇ m thick film after drying: clear, high-gloss * Minimum temperature of the dispersion required for film formation: 7-8 °
• Example X The procedure is as in Example X, the resin melt preparation to be dispersed being composed of 72 parts of a diglycidyl ether of bisphenol A with an epoxide equivalent weight of 190 g / eq (Epikote 828 from Shell), 72 parts of a diglycidyl ether of bisphenol A with an epoxide equivalent weight of 475 g / eq (Shell's Epikote 1001), 388 parts of a bisphenol A diglycidyl ether with an epoxy equivalent weight of 870 g / eq (Shell's Epikote 1004) and 200 parts of the emulsifier described in Example IV.
• the initial temperature of the resin melt preparation at the start of the dispersion is 85 ° C.
• Example XII The procedure is as in Example XII, but 160 parts of the emulsifier prepared according to Example VI are now used instead of the emulsifier used there. After the amount of water required for the phase inversion of the water-in-oil into an oil-in-water emulsion has been dispersed into the resin melt preparation, the addition of further water leads to the breakdown of the dispersion in order to set the desired final concentration. About 30% of the dispersed polymer settles out in the form of a slime within 24 hours.
• Example XIV The procedure is as in Example XIV, but instead of the emulsifier used there, 182 parts ( ⁇ 25.5%) of the emulsifier prepared according to Example VII are now used.
• Properties of the resin melt preparation before dispersing * Epoxy equivalent weight: 750 g / eq * Brookfield viscosity at 60 ° C: 650000 mPas * Glass transition temperature (DSC): -1 ° C
• Example XIV The procedure is as in Example XIV, but instead of the emulsifier used there, 58 parts ( ⁇ 10%) of a polyethylene oxide-propylene oxide block copolymer with a molecular weight determined by vapor pressure osmometry of 10060 g / mol (Pluronic F108 from BASF Corp.) are used.
• the dispersion concentrate obtained in the vicinity of the phase inversion point cannot be diluted by further addition of water. Two phases are formed.
• Properties of the resin melt preparation before dispersing * Epoxy equivalent weight: 690 g / eq * Brookfield viscosity at 60 ° C: 890000 mPas * Glass transition temperature (DSC): + 10 ° C
• Example X The procedure is as in Example X, but now 95 parts of the emulsifier prepared according to Example VIII are used instead of the emulsifier used there.
• the dispersion concentrate obtained in the vicinity of the phase inversion point cannot be diluted by further addition of water. There is phase separation.
• Properties of the resin melt preparation before dispersing * Epoxy equivalent weight (potentiometric): 397 g / eq * Brookfield viscosity at 60 ° C: 45400 mPas * Glass transition temperature (DSC): -5 ° C
• Example X The procedure is as in Example X, but now 95 parts of the emulsifier prepared according to Example IX are used instead of the emulsifier used there.
• the dispersion concentrate obtained in the vicinity of the phase inversion point cannot be diluted by further addition of water.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Epoxy Resins (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (2)

Publications (2)

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• 1989
  • 1989-04-21 DE DE3913145A patent/DE3913145A1/de not_active Withdrawn
• 1990
  • 1990-04-18 US US07/510,474 patent/US5063261A/en not_active Expired - Fee Related
  • 1990-04-19 EP EP19900107430 patent/EP0393665A3/fr not_active Withdrawn
  • 1990-04-20 CA CA002015052A patent/CA2015052A1/fr not_active Abandoned

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