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WO1986002920A1 - Compositions d'impregnation et d'encollage de fibres de verre - Google Patents

Compositions d'impregnation et d'encollage de fibres de verre Download PDF

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Publication number
WO1986002920A1
WO1986002920A1 PCT/US1985/001979 US8501979W WO8602920A1 WO 1986002920 A1 WO1986002920 A1 WO 1986002920A1 US 8501979 W US8501979 W US 8501979W WO 8602920 A1 WO8602920 A1 WO 8602920A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
glass fiber
resin
copolymer
impregnant
Prior art date
Application number
PCT/US1985/001979
Other languages
English (en)
Inventor
Donn Roy Vermilion
Donald John Algrim
Donald Jack Hammond
Richard Marvin Haines
Original Assignee
Owens-Corning Fiberglas Corporation
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
Priority claimed from US06/668,112 external-priority patent/US4636437A/en
Application filed by Owens-Corning Fiberglas Corporation filed Critical Owens-Corning Fiberglas Corporation
Publication of WO1986002920A1 publication Critical patent/WO1986002920A1/fr

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Classifications

    • 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

Definitions

  • the present invention generally relates to size and impregnant compositions. More particularly, the present invention relates to size and impregnant compositions finding particular utility when sequentially 15 applied as thin coatings to glass yarns used to reinforce elastomeric products such as vehicular tires, drive belts, pulley belts or the like.
  • the thin layer of size composition serves an additional beneficial function.
  • the size composition layer therefore also serves to protect the underlying bare glass fiber from abrasive damage which could otherwise occur during processing.
  • 5 Glass fibers therefore are typically sized as formed, collected into a strand and the strand is then wound around a take-up bobbin to form a substantially cylindrical package (conventionally termed a "yarn package"). The yarn package is then air dried or subjected
  • the dried and sized strand is then usually unwound from the yarn package and brought into contact with 5 an impregnant solution of resorcinol-formaldehyde resin in combination with various latexes compatible with the size composition and the elastomeric material.
  • the impregnated strand is again dried so as to cure and set the impregnant on the external surface of the glass strand to ensure that 0 the individual sized glass fibers of the strand are adhered one to another. Subsequent twisting of the cured impregnated strands produces a glass fiber suitable for subsequent forming into cloth, rope, cord or the like to reinforce elastomeric products.
  • the impregnated glass strands Prior to actual use, however, the impregnated glass strands are typically subjected to storage and/or shipping. The impregnated glass strands are therefore potentially exposed to ambient conditions which could deleteriously affect their properties (such as tensile 0 strength) to such a degree that their use as a reinforcing medium for elastomeric products would be seriously impaired.
  • the size and impregnant system of the present invention promotes the durability of glass strands coated therewith by maintaining the durability (i.e., minimizing 5 tensile strength loss) thereof when subjected to potentially harmful ambient conditions.
  • durability is understood to mean the percent 1 loss in tensile strength when an impregnated glass fiber is exposed to an environment of 51.7°C (125°F) at 90% relative humidity for a period of two weeks. It has been discovered that particularly favorable durability properties for 5 impregnated glass fibers can be achieved utilizing sequentially applied size and impregnant compositions as disclosed herein. Particularly, tensile losses of less than about 10% are achieved when glass fibers are sequentially sized and impregnated with the compositions of
  • a further aspect of the present invention resides in the discovery that addition of a pyrrolidone-containing polymer to the size composition substantially prevents fraying of glass fibers at the ends of the yarn package.
  • the term "fraying" is meant to refer to a quantity of individual fibers in the strand
  • the size composition of the present invention solves the fraying problem described above by the addition of a water soluble pyrrolidone-containing polymer which, upon heat 0 curing, migrates to the exterior portions of the yarn package including the ends thereof to form a protective film over the individual glass fibers of the strand which substantially prevents fraying.
  • a glass fiber having a first resinous coating formed by drying an aqueous size composition of the hydrolysis product of a copolymer of a vinyl aromatic 1 monomer and aleic anhydride and a glass fiber anchoring agent in the form of an organo silicon compound.
  • a sufficient amount of a pyrrolidone-containing polymer is present in the size composition to form a protective film on the coated surface of the glass fiber to prevent "fraying".
  • the sized glass fiber is then coated with an aqueous composition comprising a vinylpyridine terpolymer, a blend of emulsifiable mineral oils, silica derivatives
  • a resorcinol-formaldehyde resin a polybutadiene latex and wax emulsion wherein the vinylpyridine terpolymer and polybutadiene latex are each emulsified with a synthetic anionic surfactant having sulfate, sulfonate or sulfosuccinate groups.
  • any suitable glass fiber is usable with the size and impregnant compositions of the present invention.
  • glass fibers shall mean fibers formed by attenuation of one or more streams of molten glass and to strands formed when such glass fiber filaments are 0 gathered together in forming.
  • the term shall also mean yarns and cords formed by plying and/or twisting a multiplicity of strands together and to woven and non-woven fabrics which are formed of such glass fiber strands, yarns or cords.
  • the size and impregnant compositions 5 of the present invention are usable with E-type fibers having a diameter in the range of from about 0.35 to about 0.50 mil.
  • Any suitable hydrolysis product of a copolymer of a vinyl aromatic monomer and maleic anhydride can be used in the practice of this invention.
  • Particularly preferred are hydrolyzed copolymers of a vinyl aromatic monomer and maleic anhydride wherein the vinyl aromatic monomer is styrene, the copolymers having molecular weights in the range of about 25,000 to about 50,000.
  • Such copolymers are commercially available from Monsanto Corporation under the trade name "Scripset”. More particularly preferred are the half amide/half ammonium salt hydrolysis product of a copolymer of styrene and maleic anhydride having the formula:
  • Copolymers of the >above formula are commercially available from Monsanto Corporation under the trade name "Scripset 720" and have a molecular weight of about 50,000.
  • the size composition is formulated to include at least one glass fiber anchoring agent in the form of an organo silicon compound.
  • organo silicon compounds which include organo silanes containing one to three readily hydrolyzable groups, such as halogen (bromine, chlorine, fluorine or iodine) or alkoxy having one to six carbon atoms, such as ethoxy, ethoxy, propoxy, butoxy, etc., and containing at least one organic group attached directly to the silicon atom, with any remaining valences on the silicon atom being taken up by hydrogen.
  • such silanes tend to hydrolyze to form the corresponding silanols and/or siloxanes, and hence the anchoring agent is present in the aqueous size composition of the invention as the silane, silanol and/or siloxane.
  • the organic group or groups attached at the silicon atom can be any of a variety of groups including alkyl having 1-10 carbon atoms, such as methyl, ethyl propyl, hexyl, etc.; alkenyl containing 2-8 carbon atoms, such as vinyl, alkyl, etc.; cycloalkyl having 4-8 carbon atoms, such as cyclopentyl, cyclohexyl, etc.; aryl containing 6-15 carbon atoms, such as phenyl, naphthyl, benzyl, etc. and the halogen, amino, hydroxy, mercapto, glycidoxy or epoxy substituted derivatives thereof. It
  • organo silane contains more than one organic group
  • the various organic groups attached to the silicon atom can be the same or different from each other.
  • ethyldichlorosilane propyltrichlorosilane, n-butyl-trimethoxysilane, gamma-aminopropyltrimethoxysilane, delta-amino- but 1triethoxysilane, bis(gamma-aminopropyl)di- methoxysilane, delta-aminobutylethyldimethoxysilane, 0 beta-hydroxyethyltriethoxysilane, glycidoxypropyltrimethoxysilane, gamma- chloropropyl-trichlorosilane, vinyldichlorosilane, gamma-a inoallytrimethoxysilane, beta-amino- vinyltriethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane, 5 3-amino-cyclohexylethyl
  • organo silanes falling within the above description are gamma-aminopropyltriethox - 5 silane (commercially available from Union Carbide under the trade name "A 1100") and/or N-(beta-aminoethyl)-gamma- aminopropyltrimethoxysilane (commercially available from 1 Union Carbide under the trade name "A 1120").
  • the organo silane should be present in an amount between about .3% to about 1.0% by weight of the size composition.
  • one aspect of the present invention is the use of a pyrrolidone-containing polymer which forms a film on the sized glass fibers to thus prevent fraying of a strand containing plural sized fibers.
  • Preferred for this invention is a homopolymer of water-soluble polyvinylpyrrolidone (commercially obtained
  • Vinylpyrrolidone could also be copolymerized with other suitable unsaturated monomers in a manner well known to those in this art.
  • Representative monomers include halogen or
  • alkyl-substituted dienes such as butadiene, alkenes such as ethylene, propylene, etc. or methyl or ethyl methacrylates.
  • the resulting copolymer must however be water soluble.
  • Water solubility is an important aspect of the pyrrolidone-containing polymer component of this invention 0 as water solubility enables migration of the pyrrolidone-containing polymer to the outer surface of the sized glass fiber so as to form a protective film covering thereover when the glass fiber is dried. That is, the pyrrolidone-containing polymer migrates with water due to 5 its water solubility towards the heat source during drying of the glass fiber and forms a protective film over the glass fiber upon drying.
  • the pyrrolidone-containing polymer should be present in the size composition in an amount not less than 0 about .2% by weight and not greater than about .4% by weight. When used in amounts less than about .2% by weight it has been found that insufficient film-forming has occurred on the surface of the sized glass fiber thereby resulting in deleterious fraying predominantly at the ends 5 of the yarn package. On the other hand, greater than about .4% by weight of pyrrolidone-containing polymer in the size composition decreases the ability of the glass fiber to be 1 rewetted as by a latex derivative impregnant solution and thus insufficient application of the latex derivative impregnant composition results.
  • At least one emulsifying agent in the size composition which promotes the overall stability thereof and the wetting of the strand by lowering the surface tension of the size composition.
  • Preferred for this purpose are the polyoxyethylene
  • alkyl substituted phenols wherein the alkyl group contains six to twenty carbon atoms.
  • a particular example of a suitable emulsifying agent is a nine carbon alkyl substituted phenol commercially available from GAF Corporation under the name "Igepal C0630".
  • Any suitable lubricating agent can be employed in the practice of this invention.
  • Particularly preferred are sulfonated mineral oils commercially available from Emery Chemical under the trade name "Emerlube 7440".
  • solubilizing agents should be present in the size composition to maintain the polymer resin component in solution so that coating upon the glass fiber surface can be effected.
  • Any suitable organic and/or inorganic solubilizing agents nonreactive with the polymer resin 5 component can be employed for this purpose which maintain the size solution pH in the range of between about 10.0 to about 11.0.
  • Particularly preferred are tertiary organic bases such as triethylamine and inorganic bases such as sodium hydroxide.
  • a mixture of organic and inorganic bases as solubilizing agents.
  • the size composition of this invention When applied to glass fibers, the size composition of this invention will typically comprise about .35% by weight of the glass fibers. 5 B. THE IMPREGNANT COMPOSITION
  • emulsified with synthetic anionic surfactants having sulfate, sulfonate or sulfosuccinate groups is applied over a first coating of a resin formed by drying an aqueous size composition of the hydrolysis product of a copolymer of a vinyl aromatic monomer and maleic anhydride, tensile losses
  • suitable resorcinol-formaldehyde resin pre-condensate can be employed. Preferably, it will be produced employing from about 0.2 to about 0.8 mole of formaldehyde per mole of resorcinol and will contain a total solids content of about 75 weight percent.
  • the resorcinol-formaldehyde resin 5 pre- ⁇ ondensate will be employed in the composition in an amount within the range of from about 3.0 to about 10.0 weight percent of the residue produced by drying the composition and more preferred in an amount of about 5.0 weight percent.
  • a suitable pre-condensate can be formed as demonstrated hereinafter and suitable materials are available commercially, such as "Schenectady SRF 1524" available from Schenectady Chemicals.
  • any suitable vinylpyridine terpolymer which is 5 emulsified with a synthetic anionic surfactant having sulfate, sulfonate or sulfosuccinate groups can be used in 1 accordance with the present invention.
  • the terpolymer is formed directly by emulsion polymerization according to known techniques.
  • the vinylpyridine terpolymer will be a terpolymer latex of butadiene, styrene and vinylpyridine comprised of about 10-15% by weight of vinylpyridine, about 15% by weight of styrene and the balance being butadiene.
  • the vinylpyridine will preferably be employed in an amount between about 15-60% by weight of the residue produced by drying the
  • Particularly preferred vinylpyridine terpolymers emulsified in synthetic anionic surfactants having sulfate, sulfonate or sulfosuccinate groups are "Gentac 134" and "Gentac 135" available from DiversiTech General Corporation
  • any suitable polybutadiene latex which is also 0 emulsified with a synthetic anionic surfactant having sulfate, sulfonate or sulfosuccinate groups can be employed.
  • the polybutadiene latex will have an average molecular weight of between 10,000 to about 2,000,000.
  • the butadiene latex will be present in the 5 impregnant composition in an amount between 30 to 80% by weight of the residue produced by drying the composition.
  • the solubility of the butadiene latex when a dry film thereof is covered with toluene for four days is preferably in the range of 18% to 50% solids in an aliquot of the 0 toluene.
  • the butadiene latex should preferably have an inherent viscosity of at least about .55 and preferably not greater 5 than 2.0, with about .58 to about .70 being particularly preferred. 1
  • the term "inherent viscosity" is meant to refer to the inherent viscosity of a toluene solvent when a film of the butadiene latex is covered with toluene for a period of four days as expressed by the
  • Suitable anionic surfactants of the type called for herein include sulfates, sulfonates and sulfosuccinates 20 of sodium, potassium or ammonium with sodium dodecyl sulfonate and sodium decyl sulfate being particularly preferred.
  • wax emulsion typically contains about 55% solids and 5 is comprised of about 37.5% by weight microcrystalline paraffin wax ("Shell Wax 270" available from Shell Oil
  • Any suitable thickening agent can be employed.
  • Preferred thickening agents are copolymers and terpolymers of methacrylic acid and other suitable monomers, such as butadiene.
  • the thickening agent is employed in an amount 5 sufficient to increase the viscosity of the impregnant solution to aid in processing and will typically be employed in an amount of between about 0.1 to about 1.0 weight percent of the residue produced by drying the composition.
  • a particularly suitable thickening agent is "Ty ⁇ hem 68-705", commercially available from Reichhold 5 Polymers Inc., Dover, Delaware. It may be desirable to additionally employ a defoaming agent. Suitable defoaming agents are Drew Y-250 and Quaker MRL-1.
  • Any suitable blend of emulsifiable mineral oils, silica derivatives, and esters can be employed. 10. Preferably, it will be employed in an amount of from about 0.1 to about 1.0 weight percent of the residue produced by drying the composition.
  • a particularly suitable blend of emulsifiable mineral oils, silica derivatives and esters is designated "Quaker MRL-1" available from Alkaril Chemical 15 Company of Atlanta, Georgia.
  • the impregnant of this invention will also preferably contain about 1 weight percent formaldehyde, about 0.9 weight percent ammonium hydroxide and about 0.1 weight percent potassium hydroxide. 0 hen used as an impregnant for glass fibers, the dried residue will typically comprise about 17.0% by weight of the glass fibers.
  • a preferred resin size composition is prepared by 0 initially charging 35 parts of demineralized water into an agitated main mix tank. The following premixes are separately accomplished:
  • Premix I An agitated premix tank is charged with 14 parts of hot 60°C to 65.6°C (140 to 150°F) 5 demineralized water. An alkyl-substituted phenol wherein the alkyl has nine carbon atoms (Igepal CO630) is added to 1 the demineralized water in an amount of .78 parts. The mixture is agitated for five minutes and added to the demineralized water in the main mix tank.
  • Premix II To 6 parts of demineralized water 5 there is added .19 part of triethylamine and the mixture is agitated for one minute before addition to the main mix tank.
  • Premix III To 9 parts of demineralized water in an agitated premix tank there is added 3.15 parts of 10. Scripset 720 (25% resin solution). Agitation is continued for two minutes prior to addition to the main mix tank.
  • Premix IV .94 part of a sulfonated mineral oil (Emerlube 7440) is added to 9 parts of demineralized water and agitated for two minutes prior to addition to the main 15 mix tank.
  • Emerlube 7440 a sulfonated mineral oil
  • Premix V A 28% solution of ammonium hydroxide in the amount of .47 part is added to 6 parts of demineralized water and agitated for one minute prior to addition to the main mix tank.
  • Premix VI .84 part and .13 part of commercially available organo silane compounds A1100 and A1120 are respectively added to 15 parts of demineralized water and agitated for 30 seconds prior to addition to the main mix tank. 5
  • the previously-added 35 parts of demineralized water and Premixes I-VI are agitated in the main mix tank for fifteen minutes after an additional amount of demineralized water is added thereto as needed to formulate 100 parts of the size composition.
  • the percent solids in 0 main mix tank will be 3.0 + " .15 and the pH will be in the range of 10.0-11.0.
  • EXAMPLE II Formulation of a preferred impregnant composition is as follows: 5 A resorcinol-formaldehyde resin premix solution is prepared by charging 3.5 parts of deionized water into a premix tank and adding 3.05 parts of commercial resorcinol-formaldehyde premix (SRF-1524). The mixture is agitated for three minutes. Formaldehyde in an amount of 0.9 part is added and agitation is continued for thirty minutes. Thereupon, .18 part of potassium hydroxide is added followed by the addition of 3.05 parts deionized water and agitation was continued for 20 minutes from the addition of the potassium hydroxide.
  • SRF-1524 commercial resorcinol-formaldehyde premix
  • butadiene-styrene vinylpyridine latex produced by emulsion polymerization with a sulfate-containing surfactant (Gentac 134) and 4.88 parts of a wax emulsion (CX 364) are introduced. The mixture is agitated for 3 minutes. Ammonium hydroxide in the amount of .92 parts is added to
  • the impregnant 0 After aging for about three days, the impregnant 0 is suitable for use and will have a pH between about
  • the impregnant of this invention is applied to glass fibers in the usual manner, such as by way of a 5 solvent bushing or other conventional means, such as by immersion of the bundles of glass fibers in a bath of aqueous impregnating composition.
  • immersion may be accomplished by utilizing an apparatus providing a means for advancing a glass fiber bundle over a guide roller for passage downwardly into the bath containing the 5 impregnating composition, and a means for passing the bundles under a roller to effect a sharp bend which operates to open the bundle to enable fuller penetration of the aqueous impregnating composition into the bundle of sized fibers for fuller impregnation of the bundle.
  • impregnated bundle may then be raised from the bath for passage through a roller or die which operates to move excess impregnating composition from the bundle and to work the impregnating composition into the bundle. After application of the impregnant to the glass strand, the
  • impregnant is air dried and cured in the usual manner, that is, for example, at 260°C to 343.3°C (500° to 650°F) for a period of about 5 to 10 seconds.
  • Emerlube 7440 (mineral oil) 0.48%
  • FRS-272 latex (polybutadiene homopolymer) 55.0% 15 Ammonium hydroxide 0.93%
  • Tychem 68-705 thickener-polymethacrylic acid 0.45% 0 Quaker MRL-1 (defoamer) 0.38%
  • Example II A size composition in accordance with Example I herein and an impregnant composition in accordance with Example II herein. 0
  • Each sample is tested for tensile strength after curing and the data is recorded as "Strength 1". Thereafter, each sample is then subjected to an environment controlled at 51.7°C (125°F) and 90% relative humidity for two weeks. Each sample is again tested for tensile 5 strength and the data is recorded as "Strength 2". The results appear below in TABLE 3.
  • the Goodyear Hot "U” testing procedure is an adhesion test which generally involves imbedding a loop of cord into rubber and pulling an end of the loop out of the rubber.
  • Sample Nos. 1 and 3 of Example III above are formed 5 into vehicular tires and are mounted onto standard factory automobiles. The automobile is loaded with lead weights to achieve a weight equivalent to 100% of the tire and rim -13-
  • the automobiles are then maneuvered around a figure-eight course having circular centerpoints spaced apart by about 20 m (66 feet). The automobile is accelerated to a speed whereby one lap of the figure-eight
  • the size solutions A-E are each coated upon a 5 glass strand formed of multiple glass filaments in the manner described in Control Sample No. 1.
  • the sized strands are formed into respective substantially cylindrical yarn packages A-E corresponding to the size solutions A-E and oven dried.
  • the dried yarn packages are 0 then visually inspected for fraying at the ends of the yarn package with the following results:
  • the glass strands of yarn packages A-E are then 5 brought into contact with an impregnant composition designated "IC(control)" in Example III herein.
  • the impregnated strands of yarn packages A-E are cured in the 1 usual manner, e.g., at 260°C to 343.3°C (500° to 650°F) for a period of about 5 to 10 seconds and the cured impregnated strands are visually inspected to determine the amount of impregnant solution pick-up (i.e., wetability).
  • the 5 results are shown below:
  • the present invention is preferably industrially exploited by sequentially applying the size and impregnant compositions as coatings to glass fibers and yarns used to reinforce elastomeric products such as vehicular tires,
  • the formulations of the present invention impart particularly favorable durability properties to fibers sequentially sized and impregnated with the compositions of this invention.
  • composition has been found to substantially prevent fraying of glass fibers at the ends of yarn packages.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Reinforced Plastic Materials (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Abstract

Une composition d'encollage de revêtement pour des fibres de verre comprend une solution aqueuse d'une résine formée par un copolymère du produit de l'hydrolyse d'un monomère aromatique vinyle et d'anhydride maléique, et par un agent organosilane d'ancrage des fibres de verre. On obtient des propriétés de perte d'extension particulièrement favorables en appliquant un deuxième revêtement d'imprégnation aux fibres de verre encollées; le revêtement d'imprégnation est obtenu en éliminant l'eau d'une solution aqueuse d'un terpolymère de vinylpyridine, d'un mélange d'huiles minérales émulsifiables, de dérivés et d'esters de silice, d'une résine de résorcinol-formaldéhyde, de latex de polybutadiène et d'une émulsion de cire, dans laquelle le terpolymère de vinylpyridine et le latex de butadiène sont émulsifiés avec un agent tensio-actif anionique synthétique ayant un groupe sulfate, sulfone ou sulfosuccinate.
PCT/US1985/001979 1984-11-05 1985-10-15 Compositions d'impregnation et d'encollage de fibres de verre WO1986002920A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US66811384A 1984-11-05 1984-11-05
US668,112 1984-11-05
US668,113 1984-11-05
US06/668,112 US4636437A (en) 1984-11-05 1984-11-05 Glass fiber size and impregnant compositions

Publications (1)

Publication Number Publication Date
WO1986002920A1 true WO1986002920A1 (fr) 1986-05-22

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CN (1) CN85108966A (fr)
AU (1) AU5017985A (fr)
WO (1) WO1986002920A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006058237A3 (fr) * 2004-11-24 2006-11-09 Corning Inc Substrats revetus de polymere destines a fixer des biomolecules et procedes de fabrication et d'utilisation correspondants
US7781203B2 (en) 2005-12-29 2010-08-24 Corning Incorporated Supports for assaying analytes and methods of making and using thereof
CN112495317A (zh) * 2020-11-10 2021-03-16 中钢集团马鞍山矿山研究总院股份有限公司 一种连续化制备碳气凝胶前驱体的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101736589B (zh) * 2009-12-08 2012-01-25 南京信息工程大学 耐热阻燃型工业保温用玻纤制品及其制备方法
CN102877366B (zh) * 2012-09-28 2015-04-22 山东圣泉新材料股份有限公司 一种湿帘纸的制备方法
CN112839772A (zh) * 2018-10-09 2021-05-25 3M创新有限公司 经处理的背衬和包括该经处理的背衬的经涂覆的磨料制品

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3414432A (en) * 1965-10-04 1968-12-03 Exxon Research Engineering Co Sizing glass fibers with polybutadienedicarboxylic acid anhydride amino salt adducts
FR2406613A1 (fr) * 1977-10-21 1979-05-18 Owens Corning Fiberglass Corp Composition d'impregnation pour nappes cablees de pneumatiques
EP0025979A1 (fr) * 1979-09-22 1981-04-01 Hoechst Aktiengesellschaft Solution ou dispersion aqueuse d'un copolymère de styrène-anhydride maléique, procédé pour sa préparation et son utilisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3414432A (en) * 1965-10-04 1968-12-03 Exxon Research Engineering Co Sizing glass fibers with polybutadienedicarboxylic acid anhydride amino salt adducts
FR2406613A1 (fr) * 1977-10-21 1979-05-18 Owens Corning Fiberglass Corp Composition d'impregnation pour nappes cablees de pneumatiques
EP0025979A1 (fr) * 1979-09-22 1981-04-01 Hoechst Aktiengesellschaft Solution ou dispersion aqueuse d'un copolymère de styrène-anhydride maléique, procédé pour sa préparation et son utilisation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006058237A3 (fr) * 2004-11-24 2006-11-09 Corning Inc Substrats revetus de polymere destines a fixer des biomolecules et procedes de fabrication et d'utilisation correspondants
US7781203B2 (en) 2005-12-29 2010-08-24 Corning Incorporated Supports for assaying analytes and methods of making and using thereof
US7981665B2 (en) 2005-12-29 2011-07-19 Corning Incorporated Supports for assaying analytes and methods of making and using thereof
US8168399B2 (en) 2005-12-29 2012-05-01 Corning Incorporated Supports for assaying analytes and methods of making and using thereof
CN112495317A (zh) * 2020-11-10 2021-03-16 中钢集团马鞍山矿山研究总院股份有限公司 一种连续化制备碳气凝胶前驱体的方法

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EP0199763A1 (fr) 1986-11-05
AU5017985A (en) 1986-06-03

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