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WO1999040148A1 - Procede de fabrication d'une matiere preimpregnee - Google Patents

Procede de fabrication d'une matiere preimpregnee Download PDF

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Publication number
WO1999040148A1
WO1999040148A1 PCT/HU1999/000009 HU9900009W WO9940148A1 WO 1999040148 A1 WO1999040148 A1 WO 1999040148A1 HU 9900009 W HU9900009 W HU 9900009W WO 9940148 A1 WO9940148 A1 WO 9940148A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
phenol
paper
product
glass
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/HU1999/000009
Other languages
English (en)
Inventor
László DUDÁS
Géza Kecskeméthy
István KOVÁCSAY
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to AU24357/99A priority Critical patent/AU2435799A/en
Publication of WO1999040148A1 publication Critical patent/WO1999040148A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention relates to the manufacturing procedure of a preimpregnated material/sheet, also known as "pre-preg", prepared from thermosetting resins, preferably from phenol/furan resins and glass fibres, preferably from glass cloth and glassmat, to achieve an improved heat and flame resistance.
  • pre-preg prepared from thermosetting resins, preferably from phenol/furan resins and glass fibres, preferably from glass cloth and glassmat, to achieve an improved heat and flame resistance.
  • Preimpregnated materials have been used for a long time for the preparation of final products made of phenol, epoxy and polyester resins and reinforced fibres.
  • Preimpregnated materials are for example paper, natural fibre, i.e. cotton cloth and glass cloth impregnated by resins. These products are prepared in such a way that the resin, either in its natural form or diluted by solvents, for example by ethanol, is applied to the reinforced material by smearing. Following this the solvent, or the water in the resin, especially in the phenol resin, is removed by drying, and at the same time the resin is transformed into the "B" stage. In this stage the resin is not liquid any more, but by the effect of pressure and heat again it melts and forms cross-links.
  • the paper-bakelite and the textile-bakelite sheets are prepared with this method. Final products are pressed at 4- 15 Mpa and at 150-200 °C.
  • the aim of the present invention is to work out a method of preparing pre-preg being suitable for products having an improved heat and flame resistance, even in case of applying low pressure and temperature values on course of the progress.
  • a filled resin system is applied, catalysts are used, while the technology is solvent-free, drying operation by mechanical means is avoided further a mechanical impregnation step promoted by vibration caused by apparatus is carried out.
  • the catalysts are organic acids, which are hardly dissolving in water, make the water-content of the resin acidic, and this way initiate the formation of cross-links.
  • the invention is based on the discovery, that if the water is gradually removed from the resin system having a slowly dissolving catalyst, then while the mass of the catalyst remains constant, the reaction slows down, and in case of an appropriate ratio the "B" stage is formed chemically.
  • the reduction of the water content of the resin is advantageously carried out by a hygroscopic type relais foil which absorbs the water from the adjoining resin layer.
  • the application of the filled resins to one or both sides of the reinforced cloth is carried out by an exactly adjustable volumetric displacement pump. The penetration of the filled resin is assisted mechanically with vibrating edges.
  • the foil of direct water- absorbing effect can optionally be replaced by a plastic foil.
  • the impregnated material/sheet is rolled up immediately at the end of the manufacturing procedure, and the water-content is removed at the edge of the rolls by heat or vacuum.
  • furan resins having better heat and flame resistance properties than phenol resins can not get into a amidB" stage in a similar way, i.e. by a simple drying step as phenol resins can get it.
  • the reaction can not stopped, i.e. keeping a stableußB" stage in which the resin could be stored in a partially cured state, can not be archieved.
  • the furan resin can become suitable for preparing pre-preg corresponding to the aim if the invention.
  • the base of the resin matrix is made of 1-99% or 99-1% phenol and/or furan resin. Slowly dissolving organic acids are mixed into this base in 0,01-10% ratio. These acids can be the followings: hexahydrophthalic acid anhydride, phthalic acid anhydride, maleic acid anhydride, oxalic acid, or compounds similar to these.
  • fillers are put into this resin-mixture, for example aluminium hydroxide (10-50%), quartz flour (10-150%), perlit-flour (5-20%), carbon flake (0,5-5%).
  • the mixture prepared from these ingredients is smeared to one or both sides of the continuously advancing reinforcing cloth.
  • a volumetric displacement pump for example a gear pump or piston pump, as a function of the width and speed.
  • a relaise foil is applied to one or both surfaces of the impregnate material, which advances together with the impegnate material.
  • the relaise foil can be paper coated by silicone resin, polypropylene, polyethylene foil.
  • After the resin application the product is compacted with vibrating edges (10-10000 Hz, 0,1-15 mm amplitude, 1-5 mm width).
  • the reinforced material impregnated this way is immediately rolled up, together with the relais foil.
  • the diameter of the roll is 100-500 mm, the length of the rolls, that is the width of the product is 100-3000 mm.
  • the thickness of the impregnate, as a function of the reinforced material and the resin mixture, is generally 0,1-5 mm.
  • the thickness of the paper must be enough to absorb considerable amount of the water content of the resin.
  • a siliconised paper of 50 g/m 2 can absorb 40 g water per m 2 . This means for example, that from the resin layer with about 300 g water content, most of the water content (about 10- 15%) is removed by the siliconised paper in a relatively short time. In parallel with this procedure the presence of the acidic water is decreasing, and the chemical reaction slows down. By keeping the ratio mentioned above, the resin at 20 °C in 5-10 days, in roll, without any drying, gets into the "B" stage.
  • plastic for example polyethylene or polypropylene foils the water slowly leaves, and the progress of the crosslinks continues until the "B" stage.
  • the removal of the water is happening at the edges of the roll, but in considerably longer time.
  • water-absorbing, preferably siliconized paper at 20 °C the so called maturation time is about 7-14 days, but by using plastic foil it can reach 30-40 days.
  • the mixture is applied by a gear pump to the advancing relaise foil through a dispenser head, in equal thickness. 500 g/m 2 glass math is continuously applied to this layer. 200 mm after the application point a crosswise hard plastic, preferably textile bakelite sheet of 5 mm thickness is used with 3000/min frequency and 2 mm amplitude to promote the penetration of the fillers.
  • the advancing foil is 60 g/m 2 bioriented polypropylene.
  • the procedure of the Example 1 is used with the following differences.
  • the relaise foil is a 100 g/m 2 siliconized paper.
  • the resin is applied to the glass mat through two dispenser heads, one of them is applying the resin to the relaise foil under the glass mat, and the other is applying the resin from above to the glass mat.
  • the filler content of the resin increased with 20% talc.
  • the product manufactured according to the above examples can be processed with very low pressure (10-1200 kPa).
  • the processing temperature can be selected between 80-150 °C.
  • the advantages of the procedure of the present invention can be summarized in the following.
  • the pre-preg containing reinforced material (paper, cloth, etc.) and phenol- furan type impregnating material can be prepared on an extremely small machine, without any drying tunnel.
  • the pre-preg can be manufactured in industrial scale on 3-4 m long machine, with 5-20 m/min speed.
  • pre-pre products having superior heat and flame resistance properties can be made from pre-pre according to the invention compared to those consisting of phenol resins.
  • a pre-pre layer consisting of 4 pre-pre layers having 0,3 mm thickness each placed in a wood door of 55 mm thickness has ensure fire resistance for one hour, according to ISO.
  • the pre-preg according to the present invention can be applied in chimneys on a lasting loading of 350° as well.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un procédé permettant de fabriquer une matière/feuille préimprégnée, également dénommée 'préimprégnée', à partir de résines thermodurcissables, de préférence des résines phénoliques/furanniques et des fibres de verre, lesquelles proviennent idéalement d'un tissu de verre ou d'un matelas de fibres de verre. Cette résine renferme un catalyseur qui se dissous difficilement dans l'eau, ce qui permet de passer à l'étape suivante. Selon cette invention, la fabrication de ce produit ne nécessite aucun séchage: ce produit peut donc être produit par une petite machine, ce qui permet de diminuer la pollution atmosphérique. Selon le procédé de cette invention, on peut utiliser des systèmes de résines phénoliques/furanniques présentant une teneur en rembourrage élevée, ce qui permet d'améliorer considérablement la qualité du produit.
PCT/HU1999/000009 1998-02-03 1999-02-02 Procede de fabrication d'une matiere preimpregnee Ceased WO1999040148A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24357/99A AU2435799A (en) 1998-02-03 1999-02-02 Method for the preparation of preimpregnated material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HUP9800200 1998-02-03
HU9800200A HU9800200D0 (en) 1998-02-03 1998-02-03 Method for producing of thermosetting resin prepreg system

Publications (1)

Publication Number Publication Date
WO1999040148A1 true WO1999040148A1 (fr) 1999-08-12

Family

ID=89996068

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/HU1999/000009 Ceased WO1999040148A1 (fr) 1998-02-03 1999-02-02 Procede de fabrication d'une matiere preimpregnee

Country Status (3)

Country Link
AU (1) AU2435799A (fr)
HU (1) HU9800200D0 (fr)
WO (1) WO1999040148A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2124126A1 (en) * 1971-05-14 1972-11-23 Gewerkschaft Keramchemie, 5433 Siershahn Moulding prepns - contg copolymers of phenol, formaldehyde and furfuryl alcohol, resistant to heat, acids, alkalis and solvents
US4076873A (en) * 1974-07-29 1978-02-28 Shea Lawrence E Resorcinol-aldehyde resins used to bind reinforcing materials such as glass fibers in shaped object form
EP0265604A2 (fr) * 1986-10-31 1988-05-04 Rütgerswerke Aktiengesellschaft Procédé de préparation et application des résines phénoliques modifiées.
WO1994017999A1 (fr) * 1993-02-11 1994-08-18 College De La Region De L'amiante Procede de production d'un materiau composite pre-impregne

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2124126A1 (en) * 1971-05-14 1972-11-23 Gewerkschaft Keramchemie, 5433 Siershahn Moulding prepns - contg copolymers of phenol, formaldehyde and furfuryl alcohol, resistant to heat, acids, alkalis and solvents
US4076873A (en) * 1974-07-29 1978-02-28 Shea Lawrence E Resorcinol-aldehyde resins used to bind reinforcing materials such as glass fibers in shaped object form
EP0265604A2 (fr) * 1986-10-31 1988-05-04 Rütgerswerke Aktiengesellschaft Procédé de préparation et application des résines phénoliques modifiées.
WO1994017999A1 (fr) * 1993-02-11 1994-08-18 College De La Region De L'amiante Procede de production d'un materiau composite pre-impregne

Also Published As

Publication number Publication date
HU9800200D0 (en) 1998-03-30
AU2435799A (en) 1999-08-23

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