EP0882091A1 - Ungesättigte polyesterharze, flammgehemmt durch melamin- und phosphorverbindungen - Google Patents
Ungesättigte polyesterharze, flammgehemmt durch melamin- und phosphorverbindungenInfo
- Publication number
- EP0882091A1 EP0882091A1 EP97904653A EP97904653A EP0882091A1 EP 0882091 A1 EP0882091 A1 EP 0882091A1 EP 97904653 A EP97904653 A EP 97904653A EP 97904653 A EP97904653 A EP 97904653A EP 0882091 A1 EP0882091 A1 EP 0882091A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- melamine
- phosphate
- acid
- resin composition
- composition according
- 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.)
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- 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
Definitions
- the present invention relates to flame retardant unsaturated polyester resin compositions with superior flame retardant characteristics.
- Unsaturated ther osetting resin compositions generally comprise a mixture of an unsaturated resin component with an unsaturated compound copolymerisable therewith.
- Unsaturated polyester resins, crosslinked by vinyl group containing compounds, such as vinylaromatic and/or esterified ⁇ , ⁇ -unsaturated carboxylic acid compounds comprise an important class of unsaturated thermosetting resins. Generally these resins have a poor resistance to flammability because of their thermal depolyme ization when exposed to the heat of a fire, with generation of highly flammable depolymerization products. In the case for instance of unsaturated resins, crosslinked with methyl methacrylate monomers, the monomer itself is evolved.
- Known flame retardant unsaturated resins encompass unsaturated polyester resins based on halogenated ingredients, such as tetrachlorophtalic anhydride, tetrabromophtalic anhydride, chlorendic anhydride, dibromoneopentyl glycol, and diallyl tetrabromophtalate. These all have the disadvantage of being of high specific gravity, an obvious disadvantage for building purposes, and when used in end- products such as small boats or aircraft. A further disadvantage of the use of the above mentioned halogenated ingredients is that they yield corrosive hydrogen halide on combustion. Still a further disadvantage of most of these is the limited photostability.
- Another family of flame retardant unsaturated resins having the same disadvantages as mentioned above are the unsaturated acrylic resins and vinyl resins incorporating units of tetrabromobisphenol-A in the backbone.
- Flame retardant unsaturated polyester resins free of halogen are also known. These are based on high loadings of mineral fillers, such as alumina trihydrate, gypsum and/or calcium carbonate. These resins also suffer the disadvantage of a high specific gravity. Moreover they often show weathering deficiencies and generally have a high viscosity prior to cure, which is undesirable from a processing point of view.
- melamine as a blowing agent has been known in intumescent paint and mastic compounding for many years.
- a small amount of melamine is employed together with a char-former, such as pentaerythritol or dipentaerythritol , and a charring catalyst, such as ammonium polyphosphate or melamine phosphate.
- a char-former such as pentaerythritol or dipentaerythritol
- a charring catalyst such as ammonium polyphosphate or melamine phosphate.
- melamine as a flame retardant ingredient in unsaturated resins
- Boockmann, DE-A-2159757 (1973) describes the use of melamine in combination with alumina trihydrate (ATH) in flame retardant unsaturated polyester resins, but requires a special imide-modified unsaturated polyester resin to obtain a satisfactory flame retardancy rating.
- Pesta, AU-B-307745 (1973) describes the use of melamine itself as a flame retardant in unsaturated polyester resins, but requires a very high loading level of melamine, i.e. 150 parts by weight relative to 100 parts of the resin.
- liquid phosphorus compounds are known as a means for reducing the viscosity of mineral filled unsaturated resins and at the same time boosting flame retardancy of the finished cured resin.
- the most commonly used phosphorus compounds for this purpose are triethyl phosphate and dimethyl methylphosponate, as discussed by Weil in the "Handbook of Organophosphorus Chemistry", R. Engel, ed. , Marcel Dekker , Inc., New York, 1992, Ch. 14, pp. 683-738.
- a disadvantage of the liquid phosphorus compounds is that they tend to interact with the commonly used accelerators, being soluble cobalt compounds and therefore tend to retard or even inhibit the curing of the unsaturated resins by generally used peroxides.
- phosphates are sometimes used in such mineral filled formulations to increase flame retardancy or reduce smoke, even if they do not reduce viscosity.
- An example of such a compound is the bicyclic phosphate of pentaerythritol, described by
- a disadvantage of the solid phosphorus compounds as flame retardants in unsaturated polyester resins is that they require the use of some halogenated flame retardant or mineral filler, such as ATH to supplement their action. This results in formulations generally having a too high density and viscosity, and showing problems of light stability and corrosivity in the case of the use of halogens.
- the flame retarded thermosetting resin composition according to the invention and comprising (A) an unsaturated polyester resin and (B) a vinyl monomer copolymerizable with said resin (A), is characterized by further comprising an effective flame retardant amount of (C) melamine and (D) a phosphorus compound.
- the resin composition according to the invention is substantially halogen-free, and/or substantially free of a char-forming additive.
- the preferred resin composition is that which is substantially free of an unesterified polyol.
- a further preferred embodiment is that in which the phosphorus compound is a liquid phosphorus ester of lower viscosity than the unsaturated polyester resin itself.
- the unsaturated polyester resin (A) of the invention is any polyester resin mainly synthesized from organic compounds containing carboxyl and alcohol groups.
- polyesters diacids and dialcohols are usually used, but up to 40 wt.-% of both types of bifunctional monomers may be replaced by higher- functional monomers or monofunctional monomers or mixtures hereof. Preferably less than 20 wt.-% of both types of bifunctional monomers is replaced by a higher- functional monomer.
- 3-10 wt.-% of one of the two types of bifunctional monomers is replaced by a trifunctional monomer in order to obtain a branched unsaturated polyester. In this manner a higher molar mass is built up within a shorter period of time.
- At least one ethylenic unsaturated diacid is used. It may be advantageous to terminate the polyester with an unsaturated monocarboxylic acid.
- Vinylester polymers a special class of polyesters, may also be used as component (A) in the composition of the invention.
- Vinylester polymers are composed of polyols and, possibly, polyacids terminated with acrylate groups, methacrylate groups or other acrylates substituted with C2-C4 alkyl groups at the ⁇ position.
- the polyols may be hydroxyl-terminated polyesters, novolak resins, or polyethers, or, for example, semi-esters of polyols modified with epoxy, isocyanate, polyamine, etc.
- the acids that can be used usually contain fewer than 30 carbon atoms, in particular fewer that 20, more in particular fewer than 10 carbon atoms.
- ethylenically unsaturated diacid an a, ⁇ - ethylenically unsaturated diacid is preferably used, for example a diacid chosen from the group comprising fumaric acid, maleic acid, chloromaleic acid, itaconic acid, mesaconic acid, citraconic acid or the corresponding esters or anhydrides.
- An ethylenically unsaturated mono- or triacid may be chosen from, for example, the group consisting of linoleic acid or the other unsaturated fatty acids, cinnamic acid, atropic acid, acrylic acid, methacrylic acid, ethacrylic acid, propacrylic acid, crotonic acid, isocrotonic acid or corresponding ester or anhydride derivatives.
- Other diacids are preferably saturated aliphatic or aromatic.
- Aliphatic and aromatic diacids are chosen from, for example, the group : succinic acid, glutaric acid, methylglutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, dihydrophthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, 3,6- endomethylene-1,2,3,6-tetrahydrophthalic acid and hexachloro-endomethylenetetrahydrophthalic acid or the corresponding ester or anhydride derivatives.
- Mono- and/or higher-functional aromatic or aliphatic carboxylic acids are chosen from, for example, the group consisting of : benzoic acid, ethylhexanoic acid, mono- or trimeric fatty acids such as stearic acid, acetic acid, propionic acid, pivalic acid, valeric acid, trimellitic acid, 1,2,3,4- butanetetracarboxylic acid, 1,2,4,5- benzenetetracarboxylic acid, 1,4 ,5,8-naphthalene- tetracarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,2,3-tricarboxylic butane, camphoric acid, naphthoic acid, toluic acid, or the corresponding ester or anhydride derivatives.
- benzoic acid ethylhexanoic acid
- mono- or trimeric fatty acids such as stearic acid, acetic acid, propionic acid, pivalic acid, vale
- the alcohols that may be used usually contain fewer than 30 carbon atoms, in particular fewer than 20 carbon atoms, although particularly ethoxylated or propoxylated bisphenol-A derivatives of polyethylene glycol and polypropylene glycol may contain higher numbers of carbon atoms.
- ethoxylated or propoxylated bisphenol-A derivatives of polyethylene glycol and polypropylene glycol may contain higher numbers of carbon atoms.
- saturated aliphatic alcohols or alcohols containing an aromatic group are used.
- Ethylenically unsaturated alcohols may also be used.
- Dialcohols are chosen from, for example, the group comprising ethylene glycol, di(ethyleneglycol) , tri(ethylene glycol), 1,2- propanediol, dipropylene glycol, 1, 3-propanediol , 1,2- butanediol, 1,3 butanediol, 1 , 4-butanediol , 2-methyl- 1 , 3-propanediol , 1, 4-pentanediol, 1, 4-hexanediol , 1,6- hexanediol, 2 ,2-dimethylpropanediol , cyclohexane-diol , 2 ,2-bis-(hydroxycyclohexyl )-propane, 1,2- trimethylolpropane monoallyl ether, pinacol, bisphenol- A ethoxylated or propoxylated with 1-20 equivalents and novolak prepolymers, if so desired partly etherified
- Mono-and higher-functional alcohols are chosen from, for example, the group comprising methanol, ethanol, 1- or 2-propanol, 1- or 2-butanol , one of the isomers of pentanol , hexanol , octanol , 2- ethylhexanol , fatty alcohols, benzyl alcohols, 1,2- di (allyloxy)-3-propanol , glycerol, 1,2 , 3-propanetriol , pentaerythritol, tris-(hydroxyethyl ) isocyanurate and novolak prepolymers, if so desired partly etherified and ethoxylated.
- Alkoxilated unsaturated acids are particularly suitable to be used as ethylenically unsaturated alcohols, for example 2-hydroxy- ethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, bis(2-hydroxy-ethyl)fumarate, but also, for example, butenediol.
- an unsaturated polyester modified with dicyclopentadienyl (DCPD) units is used as component (A), more preferably an unsaturated polyester modified with 20-35 wt.-% DCPD units.
- the polymers (A) can be manufactured in many ways, for example by melt condensation, solvent condensation with distillative removal of water, whether or not in an azeotropic mixture, by epoxy-acid reactions and other methods known to a person skilled in the art.
- the compound (B) copolymerisable with the polyester and containing one or more vinyl groups usually contains fewer than 50 carbon atoms, preferably fewer than 30 and more in particular fewer than 15, but more than 3 carbon atoms.
- the compound containing one or more vinyl groups is preferably of the vinylaromatic, vinylether, vinylester, acrylate and/or allyl type. More in particular, a vinylaromatic or acrylate compound is used, because these react quickly in the radical polymerization.
- Vinylaromatic compounds are chosen from, for example, the group comprising styrene, ⁇ -methylstyrene, o- r m-, p-methylstyrene, p-chlorostyrene, t- butylstyrene, divinylbenzene, bromostyrene, vinyl aphthalene, ⁇ -chlorostyrene and divinylnapht alene.
- Acrylate compounds are chosen from, for example, the group comprising methyl, ethyl, propyl, isopropyl, butyl, isobutyl, phenyl, and benzyl acrylate or methacrylate, 2-ethylhexyl (meth)acrylate, dihydrocyclopentadiene acrylate, cyclohexyl (meth)acrylate, butanediol (meth)acrylate, butanediol di(meth)acrylate, (meth)acrylamide, the reaction products of (meth)acrylic acid and phenyl- or cresylglycidyl ethers, propyleneglycol di(meth)acrylate, di- en triethyleneglycol di(meth)acrylate, di- en tripropyleneglycol di(meth)aer late, hexanedioldi(meth)acrylate, trimethylolpropanetri(meth)acrylate
- Vinylether, vinylester and allyl compounds are chosen from, for example, the group comprising allylphthalate, diallylphthalate, diallylisophthalate, triallylcyanurate, diallylterephthalate, ethylhexanoic vinylester, vinylacetate, vinylpropionate, vinylpivalate, vinylether, vinylversatate, vinylpropylol ether, divinyl ether, vinylbutylol ether and vinylbenzylalcohol ethers.
- compound (B) in the composition according to the invention is halogen-free.
- the composition preferably contains one or more antioxidants, such as hydroxybenzophenone, esters of salicylic acid and hydroxyphenylbenzotriazoles.
- the composition preferably contains mould release agents.
- the composition preferably contains one or more inhibitors in amounts between 0,005 and 0,2 wt.- , in particular between 0,01 and 0,1 wt.-% with respect to the total composition weight.
- Known inhibitors that may be used are for example of the quinone type.
- the initiator system is preferably chosen from the group consisting of peroxides, perketals and percarbonates.
- peroxides perketals and percarbonates.
- examples are hydrogen peroxide, benzoyl peroxide, t-butyl peroxide, t-butyl peroctoate, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, trimethylcyclohexanone perketal, methylethylketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylisobutylketone peroxide, and diacetonealcohol peroxide.
- catalysts may be added, for instance octoates or naphthenates of copper, lead, calcium, magnesium, cerium, and in particular of manganese and cobalt, or vanadium complexes. Promotors may also be added to these accelerators, for instance acetylacetone. Aromatic amines such as dimethylaniline, diethylaniline and/or dimethylparatoluidine may also be used as catalysts.
- the preferred unsaturated polyester resin (A) is halogen-free.
- Particularly preferred resin compositions are those in which the said unsaturated polyester resin (A) is an unsaturated polyester resin, substantially free of aromatic acid moeities in the backbone. These resins are for instance based on an alkylene glycol, such as propylene glycol, and a non- aromatic carboxylic acid or its anhydride, such as maleic acid (anhydride).
- Another family of preferable unsaturated resin compositions are those comprising as component (A) an unsaturated polyurethane polyacrylate or polymethacrylate resin and at least one other ethylenically unsaturated polyester copolymerisable therewith, and wherein said component (B) comprises an alkyl methacrylate monomer.
- component (A) an unsaturated polyurethane polyacrylate or polymethacrylate resin and at least one other ethylenically unsaturated polyester copolymerisable therewith, and wherein said component (B) comprises an alkyl methacrylate monomer.
- urethane (meth)acrylate resins are for instance described in US Patent 4,480,079 (1984) and in US Patent 5,126,396
- compositions according to the invention and based on these urethane (meth)acrylate resins particularly yield a high flammability resistance.
- Char- forming additives are well known in the art of flame- retardancy. These carbon-sources are generally materials having many radicals capable of entering into an esterification reaction with phosphoric acid. They generally have a high carbon content and decompose at higher temperatures than the phosphoric acid source.
- Typical examples of char-formers are starch, casein, glucose, and polyvalent alcohols, such as pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.
- the char-former free embodiment has excellent environmental resistance, and surprisingly a high flammability resistance.
- the melamine to be used as component (C) in the composition of the invention is a definite compound, 2 , 4, 6-triamino-1 , 3 , 5-triazine, a common article of commerce. It is preferably used in finely divided, in particular powdered, form. It is within the broader scope of the invention to use crude melamine and/or polycondensed melamines, such as melam, melem and melon. These are melamines with two or three triazine rings, obtainable by condensation of melamine in the presence of a suitable catalyst, such as ZnCl 2 . It is also possible to use compounds like ammeline, ammelide and their condensation products.
- the phosphorus compound (D) in the composition according to the invention is any ester of phosphorus acids, or any salt of phosphorus acids with nitrogen-based cations, or phosphoric acid itself, such as orthophosphoric acid, pyrophosphoric acid or polyphosphoric acid.
- a preferred group of phosphorus compounds because of the convenient viscosity-lowering effect, are tetracoordinate phosphorus esters having viscosities lower than that of the unsaturated resin itself.
- tetracoordinate compound is meant a compound with four atoms attached to the phosphorus atom. Examples of such volatile phosphorus esters are triethyl phosphate, dimethyl methylphosphonate, diethyl ethylphosphonate and homologs thereof.
- Another family of phosphorus compounds which, together with melamine, are effective flame retardants, in the compositions of the invention, are ammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, ethylenediamine phosphate, piperazine phosphate, piperazine pyrophosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine metaphosphate, guanidine phosphate, dicyandiamide phosphate, and/or urea phosphate.
- a phosphoric acid that is, one or more acid tetracoordinate phosphorus compounds such as orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid or a partial ester thereof such as methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, amyl acid phosphate, dibutyl acid pyrophosphate and the like, which in the presence of the melamine, will become converted to a melamine salt.
- melamine should be added in amounts equal to or in excess of the amount which will form a salt with the phosphoric acid, i.e.
- a preferred phosphoric acid is the compound known in the fertilizer art as superphosphoric acid, this being a substantially anhydrous liquid phosphoric acid with a small pyrophosphoric acid content. This acid is readily available in commerce, for example from Texas Gulf Corp.
- a particularly preferred resin composition comprises a combination of effective amounts of melamine, a volatile phosphorus ester, preferably triethyl phosphate or dimethyl methylphosphonate, and superphosphoric acid.
- a volatile phosphorus ester preferably triethyl phosphate or dimethyl methylphosphonate
- superphosphoric acid preferably equimolar amounts of melamine and superphosphoric acid are used, since this yields excellent flame retardancy and low corrosivity. Moreover flame retardant synergism is observed between the triethyl phosphate and the superphosphoric acid in such compositions.
- the preferred relative amounts for this embodiment are from 15-25 wt.-% melamine, from 5-15 wt.-% superphosphoric acid and from 0,1-5 wt.-% volatile phosphorus ester.
- a particularly preferred resin composition according to the invention comprises as component (D) a combination of a low viscosity liquid phosphorus compound chosen from the group consisting of triethyl phosphate, dimethyl methylphosphonate and homologs thereof, and a phosphorus compound chosen from the group consisting of phosphoric acid and superphosphoric acid.
- This resin composition exhibits a synergistic interaction between the two phosphorus compounds leading to superior flame retardancy.
- the unsaturated polyester resin (A) is an unsaturated polyester resin, substantially free of aromatic acid moeities in the backbone, or for resin compositions, wherein said unsaturated polyester resin (A) is a urethane (meth)acrylate resin.
- the effective quantity of melamine is in the range of 15-70 wt.-% of the total unsaturated resin composition weight.
- the preferred quantity is 20- 60 wt.-%.
- the effective quantity of the phosphorus compound is in the range of 0,25-25 wt.-% of the total unsaturated resin composition.
- the preferred quantity is 0,5-20 wt.-%. Most preferred is 2-10 wt.-%.
- the total amount of the melamine and the phosphorus compound should preferably not exceed about 70 wt.-%, otherwise the mechanical properties of the composition may be affected in a negative sense.
- the unsaturated resin can be one based on, for instance, tetrabromophthalic acid and/or tetrachlorophthalic acid, and/or chlorendic acid, and/or diol esters of these acids, and/or dibromoneopentyl glycol and/or the bis(hydroxyethyl) ether of tetrabromobisphenol-A.
- Alumina trihydrate can be used as a supplemental flame retardant or for aesthetic reasons such as to obtain an artificial marble or onyx effect.
- Other mineral fillers can be used for like reasons, for example gypsum (calcium sulfate), mica, talc, clays, and calcium carbonate.
- gypsum calcium sulfate
- a particularly advantageous feature of the compositions of the invention is the use of melamine and the phosphorus compounds mentioned above, in combination with calcium carbonate and/or calcium sulfate (gypsum), which compositions are preferred.
- Such compositions afford a particularly high level of flame retardancy. This is surprising since it is well known to the skilled person in the art of flame retardancy that for instance calcium carbonate interferes with other flame retardants.
- the preferred phosphorus compound is a neutral ester, such as for example triethyl phosphate.
- the resin composition comprises between 10-30 wt.-% of melamine, between 30-50 wt.-% of calcium carbonate and/or calcium sulfate, and between 2-10 wt.-% of phosphorus compound, all wt.-% being with respect to the total weight of the resin composition.
- compositions of the invention are even possible to use melamine, in combination with calcium carbonate and/or calcium sulfate (gypsum), without subtantial amounts of the phosphorus compounds mentioned above.
- Such compositions surprisingly yield a high level of flame retardancy, and synergism between melamine and the calcium carbonate and/or calcium sulfate is observed.
- a resin composition comprises between 20-40 wt.-% of melamine, and between 20-40 wt.-% of calcium carbonate and/or calcium sulfate, with respect to the total weight of the resin composition.
- Blending the ingredients of the composition according to the invention can be conducted by any means suitable for the uniform dispersion of a generally viscous resin with particulate solids, such as mixing in with a rotary stirrer or a Banbury mixer.
- the resin mixtures of the invention may also have other ingredients such as pigments, stabilizers, processing aids, coupling agents, lubricants, mold release agents, and electroconductive additives.
- they may contain reinforcing additives such as glass fibers, mineral fibers, carbon fibers, aramide fibers, wollastonite, and the like.
- Minor amounts of thermoplastics may also be admixed with the resin, such as low profile additives to create a smooth surface of the moulded product and reduce or prevent shrinkage upon cure.
- the invention also relates to a flame retarded intermediate comprising a resin mixture of (A) an unsaturated polyester resin, (B) a vinyl monomer copolymerizable with said resin (A), the usual additives and reinforcing fibres, the resin mixture being thickened, characterized in that, it further comprises an effective flame retardant amount of (C) melamine and (D) a phosphorus compound.
- the thickening reaction is usually effected by adding metal oxides and metal hydroxides such as MgO and Mg(0H) 2 , in an amount of 1-10 wt.-%, based on the resin mixture.
- a maturation period, during which the unsaturated polyester resin is thickened, is usually observed before the intermediate is moldable into end-products.
- Glass fibre in the form of continuous fibres or as fibres with lengths between 0,5 mm and 5 cm, is usually used as reinforcing fibre in an amount between 30 and 300 parts by weight based on the resin mixture. Additionally, polyester, carbon, aramid, and acrylic fibres, for example, may also be used.
- SMC Sheet Molding Compound
- BMC Bulk molding Compound
- TMC Thick Molding Compound
- the resin compositions according to the invention can easily be molded into end products by all known processing methods. Suitable processing methods are for instance injection molding, compression molding or a combination of the two, as well as methods such as hand layup, spray-up, filament winding and pultrusion. End products typically manufactured with the composition according to the invention are components for the transport industry, such as for instance truck or car hoods, boat hulls and bulkheads, aircraft cabin bulkheads, components for the electronical and electrical industry, such as for instance connector housings, and components for the building industry, for example large panels or profiles.
- transport industry such as for instance truck or car hoods, boat hulls and bulkheads, aircraft cabin bulkheads
- components for the electronical and electrical industry such as for instance connector housings
- components for the building industry for example large panels or profiles.
- ModarTM - 814 an unsaturated urethane methacrylate resin, containing 38-42 wt.-% of polyurethane polyacrylate polymer, 13 wt.-% of styrene, and 47 wt.-% of methyl methacrylate. Specific gravity 1,040 - 1,060 at 255°C. Obtainable from Ashland Chemical, Inc.
- VibrinTM V51-708 an aliphatic unsaturated polyester resin from propylene glycol and maleic acid, obtained from Corning Fiberglass Canada, Inc.
- SynoliteTM 0020-N-l an unsaturated polyester resin from DSM Resins, The Netherlands.
- ATH SB - 336, a medium particle size aluminum trihydrate having 64,9 wt.-% A1 2 0 3 , particle size 33 wt.-% less than 10 microns, bulk density : 0,75 g/cm 3 loose, surface area : 1,5 m 2 /g, oil absorption 23 ml/100 g of filler, 87 % TAPPI brightness from J.M.Huber Corporation.
- MicralTM - 932 a high surface area aluminum trihydrate having 64,9 wt.-% A1 2 0 3 , particle size 100% through 325 mesh, bulk density : 0,5 g/cm 3 loose, surface area : 13 m 2 /g, oil absorption 38 ml/100 g of filler, 95 % TAPPI brightness from J.M.Huber Corporation.
- Melamine - 003 a fine particle grade melamine from DSM Melamine Americas, Inc.
- Triethyl Phosphate a colorless liquid from Eastman Chemical Company.
- FyrolTM DMMP dimethyl methylphosphonate, a colorless liquid from Akzo Chemicals.
- Ammonium polyphosphate AmgardTM MC, a white powder from Albright & Wilson.
- VicronTM 15-15 a ground calcium carbonate (average particle diameter 3 ⁇ m) from Pfizer Minerals Inc.
- Examples 11, 12, 14- 18, 20, 22, 24, 26, 27 and 29 are according to the invention.
- Examples 1-10, 13, 19, 21, 23, 25, 28 and 30 are Comparative Experiments (marked with an "*" in Tables 1-2 ) .
- Test bars were made from the compositions by pouring the prepared compositions in a mould and curing in an oven at the cure temperature, given by the manufacturer of the resin. Some bars were post cured during 24 hrs at the recommended post cure temperature. Flammability was tested by subjecting the test bars to the UL-94 test (Underwriters Laboratories). The Oxygen Index (OI) values were determined according to ASTM D 2863-77.
- the UL-94 test involved preparation of 5 standard test bars with a thickness of 3,2 mm, which were ignited by a standard flame from the bottom and their post-flame-exposure "after-flame" burning times noted.
- the target rating is "VO" which means that the average after-flame time is 5 sec. or less, and no one bar burns over 10 sec. Also no flaming drip is permitted.
- Comparative Experiment 10 shows that 10 wt.-% triethyl phosphate by itself without melamine gives a complete burn in the UL-94 test. It also interferes with the cure; the resin with triethyl phosphate at 10 wt.-% is very soft (Comp. Ex. 10, Barcol hardness 2-6, compared with 38-42 without triethyl phosphate (Comp. Ex. 1)). Even as little as 2 wt.-% triethyl phosphate (Comp. Ex. 8) retards the room temperature cure perceptibly (Barcol hardness 20-22 vs. 22-25 without).
- the formulation with the melamine was more viscous (kinematic viscosity of 98,5 Stokes at room temperature whereas with ATH it was 55,4 Stokes); the ATH formulation settled much faster and required more stirring.
- a further major advantage noted with the triethyl phosphate plus melamine formulations over the triethyl phosphate plus ATH formulations is that the melamine formulations visibly give less smoke, and form a much sturdier char barrier indicating that they can bear greater heat loads than the ATH formulations.
- additives as stabilizers, colorants, processing aids, low profile additives, delustrants, fillers such as calcium carbonate and gypsum, and other flame retardants such as halogenated additives, borates, molybdates, magnesium hydroxides, stannates, other melamine salts (borate, oxalate, sulfate, pyrophosphate, and the like) which may supplement or synergise with the flame retardant additives of the invention.
- additives as stabilizers, colorants, processing aids, low profile additives, delustrants, fillers such as calcium carbonate and gypsum, and other flame retardants such as halogenated additives, borates, molybdates, magnesium hydroxides, stannates, other melamine salts (borate, oxalate, sulfate, pyrophosphate, and the like) which may supplement or synergise with the flame retardant additives of the invention.
- Example 35 is a Comparative Experiment (marked with an "*" in Table 3).
- Example 38 is a Comparative Experiment (marked with an "*" in Table 9).
- a series of four resin compositions (BMC compounds) was prepared on a Z-blade mixer from the company Werner & Pfleiderer and molded into flat plaques for investigation of flame retardant behaviour and density.
- the compositions consisted of the following basic components (in parts by weight) :
- SynoliteTM 0020-N-l an unsaturated polyester resin from DSM Resins, The Netherlands.
- SynoliteTM 7223-M-l an unsaturated polyester resin from DSM Resins, The Netherlands.
- TEP Triethyl Phosphate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 MartinalTM OL104, an Alumina Trihydrate from Fluka Chemie. ATH-1 Martinal
- Compound 38 contains 50 wt.-% ATH, based on the resin composition weight without the glass fiber reinforcement (the paste weight).
- Compounds 38, 39 and 40 contain a decreasing amount of melamine (50, 40 and 30 wt.-% on paste weight) as filler, all in combination with TEP (10 wt.-% with respect to the melamine weight).
- compound 41 comprises a combination of melamine/TEP and ATH as filler. All compounds contain 25 wt.-% of chopped glass strands.
- the compounds were compression molded (150'C, 100 bar) into flat plaques (25x25cm) of 3,2 mm thickness. From these plaques the densities were determined according to ASTM D 792-91 and samples were cut for flame retardancy tests.
- the measured flame retardant properties were the Limiting Oxygen Index (LOI, ASTM D 2863-77) and the UL94 test (vertical testing at 3,2 mm thickness). The results obtained are summarized in Table 5
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US61547196A | 1996-02-20 | 1996-02-20 | |
US615471 | 1996-02-20 | ||
PCT/NL1997/000076 WO1997031056A1 (en) | 1996-02-20 | 1997-02-19 | Unsaturated polyester resins flame retarded by melamine and phosphorus compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0882091A1 true EP0882091A1 (de) | 1998-12-09 |
Family
ID=24465513
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97904653A Withdrawn EP0882091A1 (de) | 1996-02-20 | 1997-02-19 | Ungesättigte polyesterharze, flammgehemmt durch melamin- und phosphorverbindungen |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0882091A1 (de) |
AU (1) | AU1736397A (de) |
WO (1) | WO1997031056A1 (de) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW491843B (en) * | 1997-03-04 | 2002-06-21 | Nissan Chemical Ind Ltd | 1,3,5-triazine derivative salts of polyacids comprising phosphorus, sulfur, and oxygen and process for producing the same |
ES2157722B1 (es) * | 1998-05-12 | 2002-04-16 | Univ Pais Vasco | Formulacion de resina de poliester insaturado, ignifuga, libre de halogeno. |
US6166114A (en) * | 1998-08-13 | 2000-12-26 | E. I. Du Pont De Nemours And Company | Fire and electrical resistant compositions |
DE19837701A1 (de) * | 1998-08-19 | 2000-02-24 | Basf Ag | Flammgeschützte Polyesterformmassen |
NL1013105C2 (nl) * | 1999-09-21 | 2001-03-22 | Dsm Nv | Vlamdovend mengsel. |
US6479574B1 (en) | 1999-10-21 | 2002-11-12 | Ppg Industries Ohio, Inc. | Fire retardant composition for composites |
GB0314671D0 (en) | 2003-06-24 | 2003-07-30 | W & J Leigh & Co | Intumescent coating compositions |
ES2249142B1 (es) * | 2004-06-21 | 2007-05-01 | Muros Sint Decorativos S L | Formulacion de resina de baja viscosidad, resistente al fuego y con baja toxicidad y opacidad de humos, y su metodo de fabricacion. |
DE102006049519A1 (de) * | 2006-10-20 | 2008-04-24 | Lanxess Deutschland Gmbh | Flammwidrige, härtbare Formmassen |
FR2940308B1 (fr) | 2008-12-18 | 2011-11-25 | Cray Valley Sa | Composition thermodurcissable pour pieces composites et revetements intumescents |
GB201223312D0 (en) * | 2012-12-21 | 2013-02-06 | Bpb United Kingdom Ltd | Calcium sulphate-based products |
KR101702947B1 (ko) * | 2016-01-08 | 2017-02-09 | 강병인 | 소화물질을 함유하는 수지 입자의 제조방법 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH467831A (de) * | 1966-01-10 | 1969-01-31 | Ciba Geigy | Härtbare, füllstoffhaltige, ungesättigte Polyesterharzmischungen |
US3909484A (en) * | 1973-04-16 | 1975-09-30 | Universal Rundle Corp | Flame retardant reinforced bonded articles and bonding compositions therefor |
US4257931A (en) * | 1980-01-29 | 1981-03-24 | American Cyanamid Company | Flame retardant poly(butylene terephthalate) compositions comprising melamine pyrophosphate and a phosphonate |
DE3732377A1 (de) * | 1987-09-25 | 1989-04-06 | Hoechst Ag | Flammwidrige polymere massen |
DE3842384A1 (de) * | 1988-12-16 | 1990-07-12 | Bayer Ag | Verfahren zur herstellung von polyurethanschaumstoffen |
US5250579A (en) * | 1992-09-28 | 1993-10-05 | The Dow Chemical Company | Cellular polymer containing perforated cell windows and a process for the preparation thereof |
ATA156893A (de) * | 1993-08-06 | 1997-08-15 | Chemie Linz Gmbh | Halogenfreie, flüssige flammhemmermischung für styrolhomo- und -copolymere |
-
1997
- 1997-02-19 WO PCT/NL1997/000076 patent/WO1997031056A1/en not_active Application Discontinuation
- 1997-02-19 EP EP97904653A patent/EP0882091A1/de not_active Withdrawn
- 1997-02-19 AU AU17363/97A patent/AU1736397A/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO9731056A1 * |
Also Published As
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WO1997031056A1 (en) | 1997-08-28 |
AU1736397A (en) | 1997-09-10 |
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