WO1999045061A1 - Composite ininflammable sans halogene - Google Patents

Composite ininflammable sans halogene Download PDF

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Publication number
WO1999045061A1
WO1999045061A1 PCT/DE1999/000361 DE9900361W WO9945061A1 WO 1999045061 A1 WO1999045061 A1 WO 1999045061A1 DE 9900361 W DE9900361 W DE 9900361W WO 9945061 A1 WO9945061 A1 WO 9945061A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite material
material according
mold
anhydride
resin matrix
Prior art date
Application number
PCT/DE1999/000361
Other languages
German (de)
English (en)
Inventor
Winfried Plundrich
Ernst Wipfelder
Original Assignee
Siemens Aktiengesellschaft
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 Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Priority to AU30232/99A priority Critical patent/AU3023299A/en
Priority to EP99911593A priority patent/EP1060210A1/fr
Publication of WO1999045061A1 publication Critical patent/WO1999045061A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2

Definitions

  • Composite materials based on epoxy resins and inorganic or organic reinforcement materials have successfully replaced conventional materials in many areas of technology and everyday life on the one hand because of their relatively simple and safe processing and on the other hand because of the good mechanical and chemical property values that can be achieved with them.
  • RTM technology resin transfer molding
  • a reinforcing material e.g. a glass fiber fabric is placed in a mold, which is then filled with resin. If necessary, the process is supported by pressure and / or vacuum. It can be used to manufacture large-area parts such as those used for the lightweight construction of aircraft, ships and other vehicle components, as well as housings and construction materials in the electrical and construction industries.
  • Epoxy /? Vmin and epoxy / anhydride systems are used for RTM technology.
  • Epoxy / .Amin systems have the advantage that they can be cast and hardened at room temperature. In general, however, they have to be post-cured thermally in order to be fully cured.
  • Epoxy / anhydride systems can also be processed at room temperature, but a slightly elevated temperature, e.g. B. 60 ° C, required. For widespread use, especially for vehicle components, however, such composite materials must meet the strict requirements with regard to flame resistance.
  • the fire specification applicable to plastics in rail vehicle construction is described in DIN 5510. For example 2 W is required in the S4 classification that the plastic is extinguished within 3 seconds after 3 mm of flame exposure without dripping, the diameter of the fire stain is ⁇ 20 cm and, in addition, the integral smoke density does not exceed 50%.
  • flame retardants such as. B. brominated resin components are extremely problematic because they split off large amounts of highly corrosive bromine-containing gases in the event of a disturbance, ie in the event of a fire or charring. In addition, they can form polybrominated dibenzo-dioxes and dibenzofurans during decomposition, which have a high toxicological-ecological-toxicological risk potential.
  • Other flame retardants such as antimony trioxide, are also unsuitable because they are on the list of carcinogenic chemicals.
  • Epoxy / amine or epoxy / anhydride systems and plastic systems based on unsaturated polyesters which are flame-retardant using aluminum hydroxide are known.
  • the high filler content required has a disadvantageous effect on the processability of the reaction resin and the mechanical strength of the composite material. This measure also removes the advantage of the low density of composite materials.
  • Patent applications WO96 / 23018 and DE-A 195 06 010 describe flame-retardant epoxy / anhydride casting resins, in which phosphorous and / or phosphonic acid anhydrides are added as additional reactive flame retardant components.
  • the object of the present invention is to provide a reaction resin which is suitable for RTM technology, which is easy to process and which is flame-retardant, halogen-free, without the disadvantages observed with filled reaction resins and which, in combination with fibrous reinforcing agents, mechanical high-strength composite materials delivers.
  • epoxy / anhydride systems and flame retardant components such as phosphine and / or phosphonic acid anhydrides with fibrous reinforcing agents result in high-strength, inherently flame-retardant composite materials which are ideally suited for processing by RTM technology.
  • thermoset materials show superior mechanical and chemical molding properties and offer high flame resistance even with small proportions of reactive phosphorus compounds.
  • compositions according to the invention can advantageously be processed in the RTM process, since they have a long, adjustable service life even at elevated processing temperatures.
  • An increased processing temperature also offers favorable flow and impregnation behavior due to the lowering of the viscosity.
  • additive flame retardants e.g. Aluminum hydroxide can provide flame retardant low density composites.
  • the basic mechanical structure of the composite material according to the invention is a fiber or woven material which contains carbon, 4 glass, textile, plastic or natural fibers, such as jute fleece can include.
  • the resin matrix comprises an epoxy / carboxylic acid anhydride mixture, a reactive organic phosphorus compound based on an acid derivative, a reaction accelerator and processing aids such as defoamers, leveling agents and adhesion promoters.
  • the reaction resin matrix based on the epoxy / anhydride system is almost freely selectable, with the proviso that the viscosity is sufficiently low for the RTM technique. However, this condition is met by a variety of epoxy / anhydride systems.
  • aromatic and cycloaliphatic polyglycidyl ethers such as bisphenol A or bisphenol F diglycidyl ether, hydrogenated bisphenol A or bisphenol F or diglycidyl ether, polyglycidyl ethers of phenol or cresol formaldehyde resins and cycloaliphatic glycidyl esters such as e.g. Hexahydrophthalic acid diglycidyl ester.
  • Cycloaliphatic ring epoxidized resins such as e.g. 3,4-epoxycyclohexyl-methyl- (3,4-epoxy) cyclohexane carboxylate and bis (3,4-epoxycyclohexyl) adipate.
  • aliphatic difunctional glycidyl ethers such as ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl diglycidyl ether, polypropylene di-glycidyl ether, cyclopyalidyl ether, polytetcydalidyl ether, polytetcydidyl ether, polytetcahydrofuryldihydrofuran such as trimethylolpropane triglycidyl ether or monofunctional aromatic glycidyl ether, such as p-tert.
  • aliphatic difunctional glycidyl ethers such as ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopen
  • liquid anhydrides based on di- and tetracarboxylic acids are used as the carboxylic acid anhydride.
  • 5 Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylenedomethylene tetrahydrophthalic anhydride are particularly suitable.
  • succinic anhydride and phthalic anhydride as well as benzene
  • 1,2,4,5-tetracarboxylic acid dianhydride, benzophenonetetracarbonic acid dianhydride and biphenyltetracarboxylic acid dianhydride can be used.
  • Organic derivatives of phosphoric acid, phosphinic acid, phosphonic acid and phosphine oxide are suitable as the reactive organic phosphorus compound.
  • R and R 1 independently of one another are an alkyl or alkenyl radical having 1 to 40 carbon atoms or a cycloaliphatic or an aryl radical and n is an integer.
  • the P-containing epoxy / anhydride system can also be admixed with low-viscosity glycidyl esters of phosphonic acid derivatives.
  • Important representatives of this class of substances are, for example, methyl, propyl or phenylphosphonic acid diglycidyl esters.
  • these last-mentioned P compounds have a relatively low phosphorus content compared to propanephosphonic acid anhydride, as can be seen from Table 1.
  • the aforementioned P-containing compounds harden together with the epoxy / anhydride system and are integrated into the resulting network of the reaction resin matrix.
  • a particularly good integration into the resin matrix is a phosphorus compound, the integration of which can take place via at least two of the reactive groups mentioned. 7
  • the ratio of the epoxy function to the anhydride function, consisting of P-free anhydride and P-containing anhydride, is 1.0: 0.7 to 1.0: 1.0, preferably between 1.0: 0.9 and 1, 0: 1.0.
  • the reactivity of the reaction resin composition is not influenced by the phosphorus-containing compound in comparison to a phosphorus-free reaction resin composition.
  • the reactivity of the entire reaction resin mass can be set using a freely selectable reaction accelerator.
  • Tertiary amines e.g. Dimethylbenzylamine or tris-dimethylamino-methylphenol, organometallic complexes or imidazoles, e.g. B. 2, 4-ethylmethylimidazole, 1-methylimidazole or 1-position cyanoethylated imidazoles, such as l-cyanoethyl-2-phenylimidazole.
  • Figure 1 shows the isothermal viscosity curve of a P-containing epoxy / anhydride system at different temperatures.
  • the mixture according to the invention shown has a P content of 2.5% by weight and an accelerator content of 1%. From the viscosity curve, e.g. derive a service life of> 3 hours at 60 ° C.
  • a sufficient service life which is particularly advantageous in the production of large modules, as is advantageous, for example, for rail vehicle construction, is achieved with an accelerator proportion of 0.1 to 5.0 percent by weight, preferably less than 1.0 percent by weight.
  • a composite material has advantageous usage properties, the resin matrix of which has a processing temperature between 20 and 60 ° C and a viscosity of less than 300 mPa at the processing temperature. s shows and which has a service life of at least one hour.
  • the composite material has the further advantage that the flame retardant by means of phosphor modification of the organic resin matrix is harmless to the environment, since no toxic substances are released in the event of fire or through charring. Due to the chemical incorporation of the phosphorus compound in the hardened resin matrix and thus in the composite material, the phosphorus compound is also built into it in an aging-resistant manner against sweating, washing out or other erosion.
  • the flame retardant properties of the composite materials according to the invention are obtained without additional, specifically heavier, inorganic additives, they also have a relatively low specific weight, so that there is preferred use for vehicle construction, in which weight reduction brings decisive advantages.
  • a phosphorus content of 3 percent m of the reaction resin matrix is obtained if the phosphorus compound m is added to the hard matrix in a proportion of 26.3, 20.3 and 10.3 percent by weight.
  • the high phosphorus content of the phosphonic acid anhydride makes it possible to add a low proportion of phosphorus compound for adequate flame protection. This ensures that the otherwise practically freely selectable epoxy / anhydride system remains virtually unchanged in its chemical-physical properties and is not adversely affected. Due to the chemical incorporation of the phosphorus component in the hardened resin matrix, the phosphorus compound functions as an active hardener component and not as an unreactive additive, which could adversely affect the properties if the dosage is too high.
  • the low content of phosphorus compound is also positive for the potential hydrolysis sensitivity of the hardened resin matrix.
  • the composite materials according to the invention show only a low water absorption of less than 0.5 percent, the typical value is 0.2 percent.
  • a composite material which is particularly suitable for the production of large-area self-supporting parts, in particular for vehicle construction, is made by additionally installing a 10 layer of a lightweight material, in particular a foam layer in a then three-layer composite material.
  • a lightweight construction material for example a foam core, is given a shape on both sides with several layers of fibrous fabric, pressed and impregnated with resin.
  • Complete filling of the mold can be achieved by filling the resin matrix under pressure and, if necessary, evacuating the mold. This clean, complete filling of the mold is supported by the low viscosity and the long service life of the reactive resin compound.
  • a suitable foam for a corresponding composite material according to the invention is obtained from polyurethane or PVC. Also honeycomb structures with fiber-reinforced reactive resin application on both sides can be easily constructed.
  • a casting mold is preferably used which, after being filled with the resin composition, can be heated to a preheating temperature of at least 60 ° C. At this pre-curing temperature, the resin mass cures to such an extent that the hardened composite material can easily be removed from the mold and cured at a higher temperature. In general, a pre-curing time of approx. 10 hours is sufficient.
  • a composite material according to the invention comprises at least one fiber-containing material which is impregnated and hardened with a resin matrix. Processing using the RTM process in the closed mold makes it possible to add other layers of it to the fiber in addition to the fiber-containing material
  • a composite material with a foam is particularly suitable for vehicle construction because of the relatively low weight and the good mechanical and heat-insulating properties obtained at the same time. For example, 11 Manufacture modules for cabins of rail vehicles from this material in a simple manner.
  • Figure 1 shows the isothermal viscosity curve of a P-containing epoxy / anhydride system
  • Figures 2 and 3 show a first (two-component) and a second (three-component) composite material in a schematic cross section
  • This reaction resin matrix which has a phosphorus content of only 3.5% phosphorus, has a service life of> 3 hours at 60 ° C.
  • the viscosity is 200 mPas.
  • Figure 1 shows the plate 1 in schematic cross section.
  • a high proportion of fibrous material 2 is sought in the composite material, which can reach up to 60 percent by volume.
  • the composite material achieves a higher mechanical strength with a higher proportion of fiber-containing material, which is only shown schematically here.
  • the hardened resin matrix is denoted by 3 in the figure.
  • carbon, textile or aramid fibers are also suitable for high strengths.
  • the cast plate which has a glass fiber content of 60% by mass, shows a glass transition temperature of 82 ° C after hardening and a glass transition temperature of 97 ° C after complete hardening.
  • the surfaces are smooth and homogeneous and can be coated well with varnish without additional post-treatment.
  • Test specimens produced from this have high mechanical strengths, e.g. E-modulus> 23 GPa (bending test according to DIN 53452) and a low water absorption according to DIN 53495 with 0.20% after 3 days at 23 ° C.
  • the fire behavior for plastics in rail vehicle construction is fulfilled according to DIN 5510-2, both with the flame protection specification according to classification S4 (afterburning time 5 sec, damage size of the flame 13 cm) and with the flue gas density according to classification SR 2 (45% light attenuation - integral over the whole Test duration).
  • This reaction resin matrix is used to produce a 58 mm thick composite material at room temperature using RTM technology, consisting of a 50 mm thick solid polyurethane foam material (arranged in the center) and with 12 layers of glass fabric on each side. After curing for 3 hours at 80 ° C, the mold can be removed.
  • thermoset material produced which results in a very good bond between the polyurethane foam core and the glass fiber-filled epoxy resin layer, fulfills the requirements as a material, e.g. for the use of car body modules for rail vehicles, with regard to
  • FIG. 2 generally shows a three-layer composite material in a schematic cross section through the layers with the foam layer 4 and the hardened reaction resin matrix with the fiber material 2.
  • This reaction resin matrix has a low viscosity of 520 mPas at 25 ° C, 220 mPas at 40 ° C and 140 mPas at 60 ° C.
  • the service life at 40 ° C is> 6 h.
  • After 4 hours of hardening at 80 ° C an easily demoldable, solid plate body with a glass transition temperature of 81 ° C is obtained.
  • Complete curing with a glass transition temperature of 91 ° C is achieved after 4 h at 100 ° C. Flame-retardant, glass fiber-reinforced molded materials produced in this way also meet the fire behavior according to DIN 5510-2.
  • Fiber-reinforced plate test bodies are also produced as described in Example 1.
  • the flame protection specification according to DIN 5510-2 is achieved with a 15 burning time of 0 sec and a damage height of 14 cm (classification S4) and an integral smoke density according to classification SR 2 (light attenuation 35%).
  • This pourable reactive resin matrix which is very easy to process at 80 ° C, has a low viscosity of 120 mPas.
  • the service life at 80 ° C is> 1 hour, at 70 ° C> 3 hours.
  • the phosphorus content is 3.5%.
  • the surface of the plate produced whose carbon fiber content is 60% by volume, is smooth and shows a homogeneous appearance. It can be coated with varnish without additional post-treatment.
  • Test specimens produced from this have high mechanical strengths, for example elastic modulus> 25 GPa (bending test according to DIN 53452) and low water absorption according to DIN 53495 with 0.18% after 3 days at 23 ° C. 16
  • the plate produced fulfills the fire behavior for plastics in rail vehicle construction according to DIN 5510-2.
  • the flame protection specification is obtained according to classification S 4, with an afterburn time of 0 sec and a flame damage size of 12 cm and a specification for smoke density according to classification SR 2 with an integral light attenuation of only 24%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un composite ininflammable dépourvu d'halogène, comportant un matériau fibreux et/ou un matériau tissé qui sont imprégnés d'une matrice résineuse et durcis. Cette matrice résineuse à base d'une résine composite époxyde/anhydride est en outre ignifugée avec des composés phosphorés à base de dérivés d'acide et s'incorporant par réaction. Le composite convient comme matériau léger dans la construction de véhicules, par exemple pour des véhicules sur rails, des carrosseries de véhicules automobiles, ainsi que pour des pièces de bateau et d'avion.
PCT/DE1999/000361 1998-03-04 1999-02-10 Composite ininflammable sans halogene WO1999045061A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU30232/99A AU3023299A (en) 1998-03-04 1999-02-10 Halogen-free flame resistant composite
EP99911593A EP1060210A1 (fr) 1998-03-04 1999-02-10 Composite ininflammable sans halogene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19809211 1998-03-04
DE19809211.3 1998-03-04

Publications (1)

Publication Number Publication Date
WO1999045061A1 true WO1999045061A1 (fr) 1999-09-10

Family

ID=7859669

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1999/000361 WO1999045061A1 (fr) 1998-03-04 1999-02-10 Composite ininflammable sans halogene

Country Status (3)

Country Link
EP (1) EP1060210A1 (fr)
AU (1) AU3023299A (fr)
WO (1) WO1999045061A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1216820A1 (fr) * 2000-12-23 2002-06-26 Trespa International B.V. Panneau formé, son procédé de fabrication et son application
US6794039B2 (en) 2000-06-23 2004-09-21 Trespa International, B.V. Flame retardant resin coating
DE102008039866A1 (de) * 2008-08-27 2010-03-04 Saertex Gmbh & Co. Kg Textile Verstärkung für die Herstellung eines faserverstärkten Kunststoffbauteils
US8188165B2 (en) 2004-12-23 2012-05-29 3M Innovative Properties Company Fire-retardant low-density epoxy composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4085247A (en) * 1971-02-11 1978-04-18 Fokker-Vfw B. V. Fire-protecting epoxy resin reinforced with glass fiber
US4380571A (en) * 1981-05-18 1983-04-19 Fmc Corporation Fire retardant epoxy resins containing 3-hydroxyalkylphosphine oxides
DE19506010A1 (de) * 1995-02-17 1996-08-22 Siemens Ag Flammwidriges Reaktionsharzsystem

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4085247A (en) * 1971-02-11 1978-04-18 Fokker-Vfw B. V. Fire-protecting epoxy resin reinforced with glass fiber
US4380571A (en) * 1981-05-18 1983-04-19 Fmc Corporation Fire retardant epoxy resins containing 3-hydroxyalkylphosphine oxides
DE19506010A1 (de) * 1995-02-17 1996-08-22 Siemens Ag Flammwidriges Reaktionsharzsystem

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6794039B2 (en) 2000-06-23 2004-09-21 Trespa International, B.V. Flame retardant resin coating
EP1216820A1 (fr) * 2000-12-23 2002-06-26 Trespa International B.V. Panneau formé, son procédé de fabrication et son application
US6833174B2 (en) 2000-12-23 2004-12-21 Trespa International B.V. Molded sheet, its use, and process for its production
US8188165B2 (en) 2004-12-23 2012-05-29 3M Innovative Properties Company Fire-retardant low-density epoxy composition
DE102008039866A1 (de) * 2008-08-27 2010-03-04 Saertex Gmbh & Co. Kg Textile Verstärkung für die Herstellung eines faserverstärkten Kunststoffbauteils

Also Published As

Publication number Publication date
AU3023299A (en) 1999-09-20
EP1060210A1 (fr) 2000-12-20

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