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WO1994013473A1 - Traitement chimique des fibres de verre - Google Patents

Traitement chimique des fibres de verre Download PDF

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Publication number
WO1994013473A1
WO1994013473A1 PCT/US1993/011722 US9311722W WO9413473A1 WO 1994013473 A1 WO1994013473 A1 WO 1994013473A1 US 9311722 W US9311722 W US 9311722W WO 9413473 A1 WO9413473 A1 WO 9413473A1
Authority
WO
WIPO (PCT)
Prior art keywords
aqueous
sizing
weight percent
basis
silane
Prior art date
Application number
PCT/US1993/011722
Other languages
English (en)
Inventor
Michael W. Klett
Original Assignee
Ppg Industries, Inc.
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 Ppg Industries, Inc. filed Critical Ppg Industries, Inc.
Priority to AU57371/94A priority Critical patent/AU5737194A/en
Publication of WO1994013473A1 publication Critical patent/WO1994013473A1/fr

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
    • 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
    • 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
    • C03C25/40—Organo-silicon compounds
    • 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
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • This invention is directed to chemical treatments, called sizings, for glass fibers which are to be incorporated into resin systems for use as reinforcement or as a solid article.
  • Fibers are useful as reinforcement in a number of different applications such as described in the Fiberglass-Reinforced Plastics Deskbook by Nicholas P. Cheremisinoff and Paul N. Cheremisinoff, Ann Arbor Science Publishers, Inc., 1979, Library of Congress Catalog Card Number 78-62293.
  • glass fibers are in filament winding.
  • filament winding continuous glass fibers impregnated with resin are wound around a steel mandrel until a desired thickness is reached.
  • the resin used depends on the properties desired in the end product, and the sizing for the glass fibers depends on the resin system which is used.
  • Useful resins for this process are the liquid phenolic resins.
  • glass fibers are pulled through a heated die where they are combined with resin. As the resin and glass pass through the die, the heat cures the resin thereby forming a solid article.
  • a common example of a pultruded article is the side rail of step ladders. These are easily recognizable since they are generally a bright color, like orange. Liquid phenolic resins are also particularly useful in pultrusion processes.
  • the objects of the invention are achieved by glass fibers having thereon a sizing which is applied in an aqueous state and then dried.
  • This sizing has, in addition to water, a ureido modified amino silane coupling agent, a polyvinyl pyrrolidone film former, and a cationic lubricant.
  • the sizing may optionally have additional silane coupling agents, lubricants, film formers and plasticizers though it is preferred that the sizing be essentially free of components such as epichlorohydrin polyamide reaction products or copolymers of a vinyl aromatic monomer and maleic anhydride.
  • Glass fibers employed in the invention may be those such as "E glass”, “S glass”, “D glass” or any of the glasses known in the art. Typical formulations of such glass fibers are disclosed in The Manufacturing Technology of Continuous Glass Fibres. Library of Congress Catalog Card Number 72-97429, by K. L. Loewenstein, Elsevier Scientific Publishing, 1973, at page 29.
  • the aqueous sizing composition is applied by sprayers, rollers, belts, or the like.
  • the sized glass fibers are gathered into bundles comprising a plurality of individual fibers, generally from 200 to more than 3000.
  • the bundles are usually wound onto a forming package and the sizing is dried at room temperature or by oven heating for a time and at a temperature which will remove the moisture from the fibers.
  • the preferred time/temperature relationship for the sizing of this invention is about 285°F (141°C) for about 10 hours.
  • the sized glass fibers generally have between about 0.05 and 5 percent of sizing composition based on the weight of the glass fiber.
  • the sizing of this invention can have, in addition to water, 10 to 35 weight percent on a non-aqueous basis of ureido modified amino silane coupling agent, 25 to 70 weight percent on a non-aqueous basis of polyvinyl pyrrolidone homopolymer film former, and 5 to 25 weight percent on a non- aqueous basis of cationic lubricant.
  • the sizing may also have 0 to 15 weight percent on a non-aqueous basis of additional silane coupling agents (though preferably the amount of additional silane present is greater than zero) such as amino functional and epoxy functional silanes.
  • the sizing may also have other lubricants and film formers, and ' 0 to 35 weight percent on a non-aqueous basis of plasticizers (though preferably the amount of plasticizer present is greater than zero) for the polyvinyl pyrrolidone film former, provided, however, that there be at least one part polyvinyl pyrrolidone to each part plasticizer on a weight basis.
  • ureido modified silane is meant the novel ureido functional silanes of U.S. Patents Nos. 3,754,971 and 4,626,560 or an amino functional silane of the following general formula:
  • Z is -R 4 -N-R5.
  • Rl R2 R3 R4 and R5 may each independently be
  • A is an alkyl or alkoxide group
  • v is an integer from 1 to 10
  • w is an integer from 0 to 10
  • x is an integer from 1 to 10
  • y is an integer from 0 to 3
  • z is either 0 or 1
  • Si is a silane atom, C a carbon atom, O an oxygen atom, N a nitrogen atom and H a hydrogen atom.
  • the preferred silane is defined by the formula: O
  • silanes which is sold in a 50 percent solution in methanol as A-1160 by Union Carbide Corporation.
  • silanes may be used in the unhydrolyzed, partially hydrolyzed or hydrolyzed form. Hydrolysis of silanes is accomplished by contact with organic acid, preferably acetic acid.
  • organic acid preferably acetic acid.
  • Polyvinyl pyrrolidone is the main film former though additional film formers may be used which are water soluble, dispersible or emulsifiable, such as starches and polyvinyl alcohols .
  • Starches which may be used include amylose-containing starches and starch mixtures derived from any starch sources including corn, wheat, potato, tapioca, waxy maize, sago, rice, hybrid starches, etc.
  • the starch components having a high amylose content e.g. 50 to 60 percent by weight, are derived from either corn starch or a hybrid corn starch.
  • the starch components having a low amylose content, e.g. 20 to 30 percent by weight are usually derived from either potato or derivatized corn starch, such as cationic, phosphatized, ethoxylated or etherified derivatives.
  • the overall amylose content of a starch mixture can vary from about 35 to about 55 percent by weight based on the total starch content.
  • starches examples include those of U.S. Patent Nos. 3,227,192; 3,265,516; and 3,887,389.
  • An example of commercially available starches which may be suitable for this invention are "Hylon” , sold by National Starch and Chemical Co., and "Amaizo 2213" sold by American Maize Products Company.
  • Polyvinyl pyrrolidone is the key film former.
  • polyvinyl pyrrolidone is meant any homopolymer obtained by the addition polymerization of a monomer which may be represented by the formula:
  • Rl, R2, R3 and R4 may each be hydrogen or lower alkyls.
  • monomers include N-vinyl-2- pyrrolidone, 5-methyl-N-vinyl-2-pyrrolidone, 4-methyl-N-vinyl-2-pyrrolidone, 5-ethyl-N-vinyl-2- pyrrolidone, 4-ethyl-N-vinyl-2-pyrrolidone, 3-methyl-N-vinyl-2-pyrrolidone, 3-ethyl-N-vinyl-2- p rrolidone, 3,3-dimethyl-N-vinyl-2-pyrrolidone, 3, 5-dimethyl-N-vinyl-2-pyrrolidone and the like.
  • the polyvinyl pyrrolidone have an average molecular weight of from about 5000 to 100,000.
  • Suitable polyvinyl pyrrolidones produced by the polymerization of N-vinyl-2-pyrrolidone are available from International Specialty Products under the trade designations PVP K-15, PVP K--0, PVP K-60 and PVP K-90 wherein the K-value identifies the viscosity grade.
  • the number average of the molecular weights for these grades is about 10,000, 40,000, 160,000 and 360,000, respectively.
  • a plasticizer may also be present for the polyvinyl pyrrolidone film former.
  • plasticizers for polyvinyl pyrrolidone are carboxymethylcellulose, cellulose acetate, polyoxyalkylene glycols, glycerin, dimethyl phthalate, diethylene glycol, dibutyl tartrate, and polyalkylene glycols.
  • the preferred plasticizer is polyethylene glycol, examples of which are available from Union Carbide Corporation under the product designations Carbowax 300 and Carbowax 400 having approximate molecular weights of 300,000 and 400,000, respectively. While essentially any cationic lubricant known in the art may be used, the preferred cationic lubricants are alkyl imidazoline derivatives.
  • n-alkyl-N-amido-alkyl imidazolines which may be formed by causing fatty acids or carboxylic acids to react with polyalkylene polyamines under conditions which produce ring closure.
  • the reaction of tetraethylene-pentamine with stearic acid is exemplary of such a reaction and the product is available under the name Cation-X ® from Lyndal Chemical Co.
  • Cation-X ® from Lyndal Chemical Co.
  • cationic lubricants which may be used alone or in combination with the alkyl imidazoline derivative include a polyamino functional polyamide resin formed normally by the condensation reaction of a polycarboxylic acid such as tetraethylene pentamine, ethylene triamine, diethylene triamine, diethylenetetramine and the like.
  • a polycarboxylic acid such as tetraethylene pentamine, ethylene triamine, diethylene triamine, diethylenetetramine and the like.
  • Versamid 140 which has an amine value of 370 to 400 and is available from General Mills.
  • Another useful cationic lubricant is the partially amidated polyamine having the trade designation Emery ® 6717 available from Henkel Corp.
  • Additional silane coupling agents may be included in the sizing utilized in this invention and include amino functional silanes like those having the formula NH2-R2-Si (ORi) z where z is an integer from 1 to 3.
  • Ri can be the same or different moieties selected from lower alkyl or aliphatic hydrocarbons having less than eight and preferably less than 5 carbon atoms, and R2 is a difunctional radical selected form the lower alkyl or aliphatic hydrocarbons having less that eight carbon atoms .
  • the corresponding hydrolysis products can also be employed, such as the corresponding silanols and/or polysiloxanes .
  • Amino functional silanes of the general type gamma- aminoalkyltrialkoxy silane may be used.
  • silane coupling agents examples include gamma- aminopropyltriethoxy silanes such as those commercially available from Union Carbide Corporation under the trade designation A-1100 silane coupling agent and A-1108 amino silane coupling agent which is modified with a lubricant.
  • Epoxy functional silanes of the general type gamma- glycidoxyalklytrialkoxy silane such as gamma-glycidoxypropyltrimethoxy silane, commercially available as Union Carbide's A-187, are also useful.
  • the sizing is essentially free of epichlorohydrin polyamide reaction products and copolymer ⁇ of a vinyl aromatic monomer and maleic anhydride.
  • the resin which may be used with fibers sized" as disclosed above are those of the liquid phenolic type.
  • liquid phenolic resins what is meant is those resins which are formed by the condensation reaction of phenols and aldehydes. Such resins are well known in the art and are described in Polymer Synthesis, by Stanley R. Sandier and Wolf Karo, volume II, chapter 2, by Academic Press, Inc., New York, NY., 1977, Library of Congress Catalog Card Number 73-2073, which is part of the series Organic Chemistry: A Series of Monographs. Volume 29.
  • phenol in addition to phenol, other phenols such as o-cresol, mixed cresols, p-tert-butylphenol, p-phenylphenol, resorcinol and cardanol may be used.
  • Aldehydes such as formaldehyde and furfural may be used.
  • Units are grams per gallon and percentages are by weight on a non-aqueous basis.
  • the preparation of sizings is well known in the art and the procedure which follows is one example of the several appropriate procedures which can be employed.
  • the procedure for preparing the above sizings is similar and the following illustrates the preparation of example A above.
  • 1200 grams of hot (120-160°F or 49-71°C) water were added to a main mix tank; the polyvinyl pyrrolidone was slowly added to the main mix tank with stirring; Carbowax 300 polyethylene glycol was dissolved in hot water and added to the main mix tank; 1000 grams of hot water were added to a second tank; 29 grams of A-1100 silane and 53 grams of A-1160 silane were added to the second tank with stirring and then transferred to the main mix tank; Cation-X ® lubricant was dispersed in hot water and then added to the main mix tank.
  • Fibers sized with the solution of example C were pultruded with a liquid phenolic resin.
  • the fibers were E-glass of "K" diameter or approximately 13 microns in diameter.
  • the fibers were sized using a roller applicator and were dried in an oven at 285°F (141°C) for 10 hours.
  • the liquid phenolic resin used was a mixture of 74 percent resorcinol-formaldehyde resin and 26 percent phenol/polymer with paraformaldehyde (phenol-formaldehyde condensate) . Both resin products are sold commercially by Indspec Chemical Corporation of Pittsburgh, PA and are designated ResorciphenTM 2026-B resin and ResorciphenTM 2074-A resin respectively.
  • the pultrusion die was maintained at a temperature of about 375-400°F (195-205°C) and the glass fibers and resin moved at about 12 inches (305 cm) per minute through the die.
  • the final product had about 72-75 weight percent glass.
  • the product had a short beam shear strength according to ASTM test No. D-2344 of 5.45 Kpsi and a flexural strength according to ASTM test No. D-790 of 128.8 Kpsi.
  • Fibers sized with the solution of example A were filament wound with liquid phenolic resin.
  • the fibers were E-glass of "T" diameter or about 23.5 microns.
  • the fibers were sized and dried as described above.
  • the resin was a mixture of phenol-formaldehyde types produced by Indspec Chemical Corporation under the trade designations PRF2 1000 and PRF2 1030FM.
  • the glass fibers with the resin were filament wound in the manner known in the art at a 54° wind angle to produce a 2 inch (51 cm) diameter pipe with a wall thickness of 0.1 inches (2.5 mm) using three complete layers of glass fibers which had a yield of 250 yards/lb.
  • the pipe was cured by heating for 2 hours at between 70 and 80°C and then for 90 minutes at 90°C.
  • the same procedure was used to produce a similar pipe using the same resin but using a different, commercially available, competitive glass fiber.
  • the commercially available glass was E-glass of approximately 23 microns in diameter. Both pipe samples were subjected to destructive crush testing to determine the point of failure.
  • the competitive glass fiber pipe failed at a load of 262 pounds while the pipe made with the fibers sized according to example A failed at a load of 393 pounds, or about 50 percent greater.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (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

Une composition aqueuse d'ensimage pour fibres de verre présente des propiétés de mise en ÷uvre, une résistance au cisaillement et une compatibilité avec les agents de renforcement à base de résine phénolique améliorées. Les fibres de verre enduites et renforcées sont utilisées en enroulement filamentaire et pultrusion, ledit revêtement étant une composition aqueuse d'ensimage se composant d'un agent de pontage à l'aminosilane modifié par uréido et d'un filmogène au pyrrolidone de polyvinyle. Ladite composition est exempte de produits de réaction épochlorohydrine-polyamide et de copolymères d'anhydride maléique et de monomère aromatique vinylique.
PCT/US1993/011722 1992-12-04 1993-12-03 Traitement chimique des fibres de verre WO1994013473A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57371/94A AU5737194A (en) 1992-12-04 1993-12-03 Chemical treatment for glass fibers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US98578192A 1992-12-04 1992-12-04
US07/985,781 1992-12-04

Publications (1)

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WO1994013473A1 true WO1994013473A1 (fr) 1994-06-23

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6320066B1 (en) 1998-10-07 2001-11-20 Bayer Aktiengesellschaft Amino-functional urea-alkoxysilanes, a method for the production thereof and their use
FR2898900A1 (fr) * 2006-03-24 2007-09-28 Saint Gobain Vetrotex Ensimage pour mat de verre aiguillete
WO2008150944A3 (fr) * 2007-06-01 2009-02-05 Ocv Intellectual Capital Llc Mat de fibres à fil coupé par voie humide
WO2009086152A3 (fr) * 2007-12-21 2009-10-15 Ocv Intellectual Capital, Llc Dispersion variable de fibres de verre à fils coupés utilisées en voie humide dans un mat à fils coupés
US7927459B2 (en) 2007-09-17 2011-04-19 Ocv Intellectual Capital, Llc Methods for improving the tear strength of mats
CN119425233A (zh) * 2024-12-03 2025-02-14 江苏润众环保材料有限公司 一种聚酯纤维pe滤袋

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249411A (en) * 1963-03-21 1966-05-03 Pittsburgh Plate Glass Co Method of forming a glass fiber reinforced resinous body
US4795678A (en) * 1985-07-02 1989-01-03 Ppg Industries, Inc. Chemically treated glass fibers
US4810576A (en) * 1985-09-30 1989-03-07 Ppg Industries, Inc. Treated glass fibers and aqueous dispersion and nonwoven mat of the glass fibers
JPH03294337A (ja) * 1990-04-13 1991-12-25 Asahi Fiber Glass Co Ltd 成形材料の製造法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249411A (en) * 1963-03-21 1966-05-03 Pittsburgh Plate Glass Co Method of forming a glass fiber reinforced resinous body
US4795678A (en) * 1985-07-02 1989-01-03 Ppg Industries, Inc. Chemically treated glass fibers
US4810576A (en) * 1985-09-30 1989-03-07 Ppg Industries, Inc. Treated glass fibers and aqueous dispersion and nonwoven mat of the glass fibers
JPH03294337A (ja) * 1990-04-13 1991-12-25 Asahi Fiber Glass Co Ltd 成形材料の製造法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6320066B1 (en) 1998-10-07 2001-11-20 Bayer Aktiengesellschaft Amino-functional urea-alkoxysilanes, a method for the production thereof and their use
FR2898900A1 (fr) * 2006-03-24 2007-09-28 Saint Gobain Vetrotex Ensimage pour mat de verre aiguillete
WO2007113425A1 (fr) * 2006-03-24 2007-10-11 Ocv Intellectual Capital, Llc Mat de verre aiguillete
WO2008150944A3 (fr) * 2007-06-01 2009-02-05 Ocv Intellectual Capital Llc Mat de fibres à fil coupé par voie humide
US8080171B2 (en) * 2007-06-01 2011-12-20 Ocv Intellectual Capital, Llc Wet-laid chopped strand fiber mat for roofing mat
US7927459B2 (en) 2007-09-17 2011-04-19 Ocv Intellectual Capital, Llc Methods for improving the tear strength of mats
WO2009086152A3 (fr) * 2007-12-21 2009-10-15 Ocv Intellectual Capital, Llc Dispersion variable de fibres de verre à fils coupés utilisées en voie humide dans un mat à fils coupés
CN119425233A (zh) * 2024-12-03 2025-02-14 江苏润众环保材料有限公司 一种聚酯纤维pe滤袋

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