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WO1996041770A2 - Granules de fibres de verre contenant des poudres polymeres - Google Patents

Granules de fibres de verre contenant des poudres polymeres Download PDF

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Publication number
WO1996041770A2
WO1996041770A2 PCT/US1996/008391 US9608391W WO9641770A2 WO 1996041770 A2 WO1996041770 A2 WO 1996041770A2 US 9608391 W US9608391 W US 9608391W WO 9641770 A2 WO9641770 A2 WO 9641770A2
Authority
WO
WIPO (PCT)
Prior art keywords
polymeric material
glass
polypropylene
glass fibers
pellets
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1996/008391
Other languages
English (en)
Other versions
WO1996041770A3 (fr
Inventor
Homer G. Hill
Christopher M. Hawkins
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Owens Corning
Original Assignee
Owens Corning
Owens Corning Fiberglas Corp
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 Owens Corning, Owens Corning Fiberglas Corp filed Critical Owens Corning
Priority to AU61481/96A priority Critical patent/AU6148196A/en
Publication of WO1996041770A2 publication Critical patent/WO1996041770A2/fr
Publication of WO1996041770A3 publication Critical patent/WO1996041770A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/026—Pelletisation or prereacting of powdered raw materials

Definitions

  • the present invention relates generally to a novel glass composition and, more particularly, to pellets produced from glass fibers by mixing hydrated glass fibers to form pellets, adding polymeric material, and drying.
  • Chopped glass strands are commonly used as reinforcement material for thermoplastic articles. Glass strands of particular lengths and diameters are added to thermoplastic resins to form such composite articles as automotive distributer caps, power hand-tool housings, fan shroud, and chain saw housings.
  • glass strands are used as a reinforcement material, larger, denser glass materials are constantly being sought.
  • One variation involves compacting the glass strands. Compacted chopped glass strands have previously been used as thermoplastic reinforcement material.
  • the prior art discloses a method for producing compacted glass strands by wetting chopped glass strands and vibrating them. However, this method is slow and produces a fiber rod which is consolidated from one chopped strand. Therefore, the diameter of the glass fiber rod of the prior art is not significantly greater than an individual chopped strand.
  • thermoplastic reinforcing glass product which is significantly denser and larger in diameter than an individual chopped strand and which can be produced efficiently.
  • a glass-containing composition comprising polymeric material and pellets produced by the process of hydrating glass fibers to achieve a water content on the glass fibers of from about 11 weight percent to about 20 weight percent, mixing the glass fibers for at least about 3 minutes, thereby forming pellets, and drying.
  • the polymeric material permeates the pellets.
  • the polymeric material is preferably a high-molecular weight polymer.
  • the polymeric material is preferably selected from the group consisting of triglycidyl isocyanurate, terephthalic acid, polypropylene, polypropylene-maleic anhydride, nylon, polycarbonate, epoxy resins, polyphenylene sulfide, polyetherketone, polyamides, polyesters, and polyurethane. More preferably, the polymeric material is selected from the group consisting of triglycidyl isocyanurate, terephthalic acid, polypropylene, and polypropylene-maleic anhydride.
  • the polymeric material may only coat the outer surface of the pellets.
  • the polymeric material is preferably a high-molecular weight polymer. More preferably, the polymeric material is selected from the group consisting of triglycidyl isocyanurate, terephthalic acid, polypropylene, polypropylene-maleic anhydride, nylon, polycarbonate, epoxy resins, polyphenylene sulfide, polyetherketone, polyamides, polyesters, and polyurethane. Most preferably, the polymeric material is selected from the group consisting of polyurethane, polypropylene, and polypropylene-maleic anhydride. In another variation, the polymeric material may both permeate the pellets and coat the outer surface of the pellets.
  • a process for producing a novel glass fiber composition comprises the steps of: hydrating glass fibers by coating the glass fibers with sufficient water to achieve a water content on the glass fibers of from about 11 weight percent to about 20 weight percent, applying polymeric material to the glass fibers, mixing the glass fibers for at least about 3 minutes, thereby forming pellets, and drying.
  • the polymeric material is applied to the glass fibers prior to pellet formation.
  • the polymeric material is preferably a high-molecular weight polymer.
  • the polymeric material is preferably selected from the group consisting of triglycidyl isocyanurate, terephthalic acid, polypropylene, polypropylene-maleic anhydride, nylon, polycarbonate, epoxy resins, polyphenylene sulfide, polyetherketone, polyamides, polyesters, and polyurethane. More preferably, the polymeric material is selected from the group consisting of triglycidyl isocyanurate, terephthalic acid, polypropylene, and polypropylene-maleic anhydride.
  • the polymeric material may be applied to the glass fibers only after pellet formation.
  • the polymeric material is preferably a high-molecular weight polymer. More preferably, the polymeric material is selected from the group consisting of triglycidyl isocyanurate, terephthalic acid, polypropylene, polypropylene-maleic anhydride, nylon, polycarbonate, epoxy resins, polyphenylene sulfide, polyetherketone, polyamides, polyesters, and polyurethane. Most preferably, the polymeric material is selected from the group consisting of polyurethane, polypropylene, and polypropylene-maleic anhydride.
  • the polymeric material may be applied to the glass fibers both prior to pellet formation and after pellet formation.
  • the glass composition does not resemble typical chopped glass strand.
  • the glass fiber composition of the present invention which is identified as a reinforcing fiber pellet (RFP), is a compact pellet-shaped material composed of a layering of many glass fibers. Polymeric material is incorporated in the RFP.
  • RFP reinforcing fiber pellet
  • RFPs are composed of glass fibers. These fibers may be selected from a wide variety of diameters and lengths. Preferably, the glass fibers have a diameter in the range of from about 8.5 microns to about 100 microns. More preferably, the glass fibers have a diameter in the range of from about 8.5 to about 34 microns. Also, fibers of more than one diameter may be used.
  • the glass fibers are preferably chopped strands. These chopped strands are preferably of a length between 1/16 inch (1.59 mm) and 1/2 inch (12.7 mm). More preferably, they are of a length between 1/8 inch (3.2 mm) and 1/4 inch (6.4 mm).
  • the glass fibers are hydrated and mixed for a sufficient period of time to produce pellets.
  • the hydration of the fibers should be sufficient to prevent filamentization of the fibers.
  • the fibers should not be excessively hydrated or the fibers will agglomerate into a useless clump.
  • the water content of the hydrated glass fibers is from about 11 weight percent to about 20 weight percent. More preferably, the water content of the hydrated glass fibers is from about 12 weight percent to about 18 weight percent. Most preferably, the water content of the hydrated glass fibers is from about 14 weight percent to about 15 weight percent.
  • the hydration solution may be water alone or may be water in combination with polymeric material.
  • Polymeric material is combined with the glass fibers in several manners.
  • polymeric material can be applied to the fibers prior to pellet formation. A preferred method of accomplishing this is to add the polymeric material to the hydrating water to form an aqueous solution. The polymeric material is then applied to the glass fibers during hydration. Alternatively, a solution containing an polymeric material such as a sizing composition can be applied to the glass fibers prior to hydration. The polymeric material can be applied to the glass in any useful form, including powders, fibers, and liquids. Second, polymeric material can be applied after the glass fiber pellets have been formed. This can be accomplished in a variety of methods including spraying and immersion. Third, polymeric material can be applied both before and after pellet formation.
  • the final glass-polymer composition may have a polymer weight percent in the range of about 0.5% to about 70%.
  • the polymeric material is preferably a high-molecular weight polymer.
  • a "high-molecular weight polymer” is defined as a large molecule, of molecular weight greater than 10,000, usually composed of repeat units of low-molecular weight species.
  • Polymeric materials which are useful in the present invention include compositions such as coupling agents, film formers, wetting agents, thickeners, binders, lubricants, and anti-static agents. Polymeric materials are preferred.
  • Specific polymers include triglycidyl isocyanurate, terephthalic acid, polypropylene, polypropylene-maleic anhydride, nylon, polycarbonate, epoxy resins, PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), polyetherketone, polyamides, polyesters, and polyurethane.
  • the hydrated glass fibers are preferably mixed for a period of time from about 3 minutes to about 15 minutes. More preferably, the glass fibers are mixed for a period of time from about 5 minutes to about 10 minutes. Most preferably, the glass fibers are mixed for a period of time from about 8 minutes to about 9 minutes.
  • the term "mixing" is used in the present invention to describe any process which will keep fibers moving over and around one another. Such processes may also be described as tumbling, agitating, 0 blending, commingling, stirring, and intermingling.
  • the glass fibers may be hydrated and mixed in a variety of methods. One method involves placing glass fibers in a plastic bag.
  • the bag is flattened, and an aqueous solution containing water and polymeric material is sprayed directly on the fibers.
  • the bag is then rotated, flattened, and liquid is once again applied. The spraying continues until the desired degree of hydration is reached.
  • the rotating process is complete when glass pellets form in the bag.
  • Other processes can also be used to hydrate and mix the glass fibers. These processes include a modified disk pelletizer, a rotating drum pelletizer, a vibrating bed, a plow mixer, and a ribbon mixer.
  • a commercially available disk pelletizer is modified and used to hydrate and mix the glass fibers.
  • a disk pelletizer operates by rotating a large, dish-shaped disk. The disk is maintained at a 25° to 30° angle.
  • Commercially available disk pelletizers have scraper blades inside the disk which prevent clumps of powder from forming.
  • the disk pelletizer is modified by removing the scraper blades from the interior of the disk and coating the interior of the disk with a non-wetting coating such as TeflonTM. The scraper blades are removed to allow the glass fibers to freely mix. The non-wetting coating is applied to prevent build-up of glass fibers on the interior surface of the disk.
  • chopped glass strands are introduced into the bottom of the modified disk.
  • the glass strands are treated with an aqueous solution as they rotate in the disk.
  • the hydrated, pelletized glass fibers are removed from the pelletizer by passing over the front lip of the disk. A continuous process is achieved as pellets fall from the disk as fiber is continuously introduced into the bottom of the modified disk.
  • the pelletized glass fibers are dried to form the glass fiber pellets of the present invention.
  • the glass fibers are dried at a temperature of from about 150°C to about 315°C. More preferably, a temperature of from about 185°C to about 300°C is used. Most preferably, a temperature of from about 200°C to about 250°C is used.
  • Drying can be accomplished in a variety of manners.
  • a preferred method uses a fluidized bed oven known as a Jeffrey oven.
  • a Jeffrey oven is a commercially available drying device.
  • other processes such as a heat tower, a cookie sheet used in a convection or microwave oven, and others may be used.
  • the resulting glass fiber product is a compact pellet-shaped material composed of a layering of many glass fibers.
  • the glass fiber pellet produced by the present invention is about 20 to 30 percent denser than an individual glass strand. Also, the glass fiber pellet produced by the present invention is about five to fifteen times larger in diameter than an individual glass strand.
  • the glass fiber pellets are useful as a reinforcing material for thermoplastics and other materials.
  • glass fiber pellets of the present invention may be used in other capacities that would be apparent to one skilled in the art.
  • the following examples are given to illustrate certain preferred details of the invention, it being understood that the details of the examples are not to be taken as in any way limiting the invention thereto.
  • Example 1 Three thousand four hundred (3400) grams of wet glass fiber are placed in a 24-inch (610 mm) by 42-inch (1067 mm) polyurethane bag. The glass fiber is wet due to forming moisture acquired during manufacture of the glass fibers. The fibers are spread out in a flat, thin layer with the bag flat on the table. A solution containing 958.5 grams of water and 41.5 grams of TGIC (triglycidyl isocyanurate) is placed in a spray bottle and applied to the glass fibers in the following manner: The flat, thin layer of glass is sprayed with solution; the bag is then flipped 180 degrees, flattened, and sprayed again. The bag is then flipped 90 degrees, flattened, and sprayed.
  • TGIC triglycidyl isocyanurate
  • the flipping, flattening, and spraying procedure is continued.
  • the bag is alternately flipped 180 degrees and then 90 degrees.
  • spraying is stopped.
  • the process is complete when glass pellets form in the bag.
  • the bag is then tied close.
  • the bagged glass fibers are dried.
  • the bagged glass fibers are slowly hand fed into a Jeffrey oven set at 205°C, screened, and boxed.
  • the resulting glass composition is pellet-shaped.
  • the glass strand pellets are of the same length as the input chopped strands. Also, the pellets do not agglomerate into larger pellets when mixed for a prolonged period of time.
  • Example 2 One hundres (100) grams of 497EE 1/8-inch (3.2 mm) chopped glass fibers, which are commercially available from Owens Corning, are placed in an empty quart-size paint can. Twenty (20) grams of Polybond 3002, a polypropylene-maleic anhydride which is commercially available from Uniroyal, is pulverized to a 125 micron powder and added to the chopped glass fibers in the paint can. A lid is placed on the can, and the can is shaken and rotated by hand to intimately mbc the powder and the chopped glass fibers. The lid is removed.
  • Polybond 3002 a polypropylene-maleic anhydride which is commercially available from Uniroyal
  • a solution containing 76 grams of Witco 290H, a polyurethane which is commercially available from Witco Corporation, and 864 grams of deionized water are placed in a spray bottle.
  • the chopped glass fibers and polymer powder are rotated in the open can while being sprayed with the Witco 290H-water solution. Spraying stops when 48 grams of solution have been applied to the fibers and polymer powder. Rotation continues until pellets are formed.
  • the pellets are removed from the can and placed in a glass dish.
  • the glass dish is placed in a standard convection oven set at 110°C to dry the pellets. When the pellets are dry, they are removed.
  • the dried pellets are very flowable with minimum fines or loose powder.
  • the final composition of the pellets is, by solids weight percent, 82% glass, 16% Polybond 3002, and 2% Witco 290H.
  • the present invention results in several advantages. RFPs exhibit much better flow and fewer fines than typical chopped-strand products. Also, sizings and binders can be applied to the glass pellets outside of the glass forming environment. Therefore, chemistries which are not desirable in the forming process because of toxicity, cleanliness, etc. can be used with this product. In addition, the pelletizing process of the present invention produces improved glass strand pellets of the same length as the input chopped strands. Furthermore, the pellets do not agglomerate into larger pellets when mixed for a prolonged period of time.
  • the polymer-containing glass pellets of the present invention have several advantages. At higher polymer percentages, the polymer-containing glass pellets can be used as a moldable composition in itself without adding additional material. In addition, polymer-containing glass pellets are stronger than glass pellets without polymer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur une composition de fibres de verre comprenant des matières polymères et des granulés que l'on fabrique de la manière suivante: hydratation des fibres de verre pour faire passer la teneur en eau des fibres d'environ 11 % en poids à environ 20 % en poids, mélange des fibres de verre pendant au moins 3 minutes, ce qui permet la formation de granulés, et séchage.
PCT/US1996/008391 1995-06-07 1996-06-03 Granules de fibres de verre contenant des poudres polymeres Ceased WO1996041770A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61481/96A AU6148196A (en) 1995-06-07 1996-06-03 Glass fiber pellets incorporating polymer powders

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47959395A 1995-06-07 1995-06-07
US08/479,593 1995-06-07

Publications (2)

Publication Number Publication Date
WO1996041770A2 true WO1996041770A2 (fr) 1996-12-27
WO1996041770A3 WO1996041770A3 (fr) 1997-05-15

Family

ID=23904635

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/008391 Ceased WO1996041770A2 (fr) 1995-06-07 1996-06-03 Granules de fibres de verre contenant des poudres polymeres

Country Status (2)

Country Link
AU (1) AU6148196A (fr)
WO (1) WO1996041770A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110903563A (zh) * 2019-11-15 2020-03-24 西安海的电子科技有限公司 一种通信光缆填充料的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3498803A (en) * 1967-04-13 1970-03-03 Corning Glass Works Glass or glass-ceramic steam treatment method and article
US3635879A (en) * 1969-11-04 1972-01-18 Monsanto Co Process for the preparation of glass concentrates in a thermoplastic matrix
AU541503B2 (en) * 1981-11-27 1985-01-10 Nitto Boseki Co. Ltd. Producing compacted chopped strands
EP0137427B1 (fr) * 1983-10-11 1990-05-16 Bayer Ag Composition d'apprêt pour fibres de verre

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110903563A (zh) * 2019-11-15 2020-03-24 西安海的电子科技有限公司 一种通信光缆填充料的制备方法

Also Published As

Publication number Publication date
AU6148196A (en) 1997-01-09
WO1996041770A3 (fr) 1997-05-15

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