CA2012573A1 - Flame-retarded reaction resin compositions - Google Patents
Flame-retarded reaction resin compositionsInfo
- Publication number
- CA2012573A1 CA2012573A1 CA002012573A CA2012573A CA2012573A1 CA 2012573 A1 CA2012573 A1 CA 2012573A1 CA 002012573 A CA002012573 A CA 002012573A CA 2012573 A CA2012573 A CA 2012573A CA 2012573 A1 CA2012573 A1 CA 2012573A1
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- Prior art keywords
- hydrogen
- reaction resin
- independently
- flame
- carbon atoms
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- 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
- C08K5/5398—Phosphorus bound to sulfur
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Fireproofing Substances (AREA)
Abstract
K-17510/+/CGW 19 Flame-retarded reaction resin compositions Abstract Reaction resin compositions containing as flame-retardant a mixture of a) a hydroxide of a metal of group 2 or 13 of the Periodic Table of Elements, and b) an organophosphorus compound of general formula I
Description
2~2~7~
K-17510/-~/CGW 19 Fhlme-retarded reaction resin compositions The present invention relates to flame-retarded reaction resin compositions containing a mixture of a metal hydroxide and an organophs)sphorus compound, and to the use of such mixtures for the flame-retardation of reaction resin compositions~
US-A-4 220 472 discloses dioxaphospl~ alle oxides as flame-proofing agents for polymers, especially for cellulose. ~lso, US-A-4 219 607 describes lligh-voltageinsulating matcrials that contaill ml additive that prevents trackillg and a phosphoms-cont;linillg compolllld as erosion islhibitor. Furthermore, US-A-4 668 7 l 8 discloses self-extit!guisllillg, track-resistal~t epo.~y resin mouldillg materials that contain aluminium hydroxide and calcium phosphate as flame-retardant components.
The flame-resistance of reaction resin materials is generally improved by reducing the proportion of organic, and therefore combustible, material, that is to say by the addition of non-combustible or difficultly combustible fillers, such as quartz powder, glass, wollastonite etc. In order to achieve adequate flame-protection, however, the proportion of filler must be very high, which often results in insoluble problems in the manufacture and processing of the reaction resin materials.
A further possibility is the addition of flame-proofing agents to the reaction resin materials. Inorganic additives, such as, for example, boron compounds or metal hydroxides, are suitable. In this case too, large proportions of such additives are necessary, which also has an adverse effect on manufacture and processing. The use of halogenated compounds, such as, for example, brominated bisphenol A epoxy resins or brominated anhydride hardeners, of which the flame-retardant action is generally assisted by a synergistic agent, for ex~m1ple Sb203, has the serious disadvantage that hydrogen halide is released on burning. Not only is hydrogen halide hazardous from a toxicological standpoint but it has an extremely high corrosion potential, which in the event of a -fire in an electrical unit, ~specially an electronic unit, could result in serious secondary damage as a result of electrochemical corrosion.
2~2~7~
The use for flame-retardation purpos~s of organophosphorus compounds that are not incorporated in the reaction resin moulding material gives rise to a form of plasticiser effect, which results in considerable loss of mechanical and electrical properties in the reaction resin moulding materials that have undergone such flame-retardant treatment. For example, the strength parnmeters and/or the glass transition temperature are reduced as a result of the plasticising effect of the organophosphorus coMpound. In addition, those compounds are generally unstable to hydrolysis, which results in the reaction resin moulding material exhibiting increased water absorption with the simultaneous fo~mation of various phosphoric acid compounds.
Surprisingly, there has now been discovered a flame-ret,lrdallt mi:cture for use in reactio resin materials that does not impair their processability and that brings about an increase in the flame-resistance of the Mouldillg m;lterials but does not h.lve illl adverse effect on their properties, sllch as therm;ll stability, tllCCh.llliC.II sLrength or water absorp~ioll The present invention relates to reaction resin compositions containing as flame-retardant a mixture of a) a hydroxide cf a metal of group 2 or 13 of the Periodic Table of Elements, and b) an organophosphorus compound of general forrnula I
R4 Rs 4 / 5 `C/ O X X O `C R
\1111/ \~ 1 R2 \CH 0/\0--C/H R2 (I), wherein X each independently of the other is oxygen or sulfur, Rl each independently of the other is hydrogen, an alkyl radical having from l to 4 carbon atoms or phenyl, R2 each independently of the other is hydrogen or an nlkyl radical having from 1 to 4 carbon atoms, or l and R~ together with the common carbon atom form a cyclohexylidene or cyclohexenylidene ring, 3 and R5 are each independently hydrogen or an alkyl radical having from 1 to 4 carbon atoms, and 2~2~
R4 each independently of the other is hydrogen or methyl, wherein at least one of the substituents R~ 2, R3, R4 and Rs is other than hydrogen, and when Rl and R2 form a ring together with the common carbon atom, R3, R4 and Rs are always hydrogen.
When Rl, R2, R3 or Rs is an allcyl radical having from 1 to 4 carbon atoms, that radical can be branched or straight-chain and is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl or tert.-butyl, but p~eferably methyl or ethyl, especially methyl.
Preferred compounds of formula I are those wherein each of Rl and R2, independently of the other, is hydrogen or alkyl having from 1 to 4 c,lrbon ntoms, or Rl and R2 together with thc common carbon atom form a cyclohexylidelle or cyclohexellylidene ring and R3, R~l and Rs are eacll hydrogen Compounds of formula I wherein Rl ~ld R2 are each alkyl having from 1 to 4 c~rbon atoms, especially methyl, are especially preferred Compounds of formula I that are very especially preferred are bis-(2-thiono-5,5-dimethyl-1,3,2-dioxaphosphinan-2-yl)-oxide and bis-(2-oxo-5 ,5-dimethyl- 1 ,3,2-dioxaphosphinan-2-yl)-oxide.
The designation of the groups in the Periodic Table of Elements corresponds to the new notation, as described in Chem. and Eng. News 63(5), 27, (1985).
The metal hydroxides suitable as component a) of the flame-retardant mixture are, for example, magnesium hydroxide, calcium hydroxide, boron hydroxide and aluminium hydroxide. Magnesium hydroxide and aluminium hydroxide or a mixture of the two hydroxides are preferred.
The preparation of components a) and b) of the flame-retardant rnixture is effected according to methods known ~ se. The metal hydroxides a) are mostly commerciallyavailable. The organophosphorus compounds can be prepared, for example, according tu the method described in US-A-4 220 472 and some of them are also commercially available.
2 ~ 3 The amounts of the individual components relative to the total weight of the reactioll resin compositions are advantageously, for component a), up to 70 % by weight, but preferably from 20 to 60 % by weight, especially from 30 to 50 % by weight; and for component b) from 2 to 40 % by weight, but preferably from 2 to 20 % by weight, especially from 5 to 15 % by weight. The content of components a) and b) together is a maximum of 85 % by weight, preferably 70 % by weight, relative to the total weight of the reaction resin compositions.
The mixture according to the invention is very suitable as a flame-retardallt for reaction resin materials. Especially suitable reaction resins nre epoxy rcsins ancl polyllrethane resins. The reaction resin compositions rendered llame-retardant according to the il~Vt~ll-tion are preferably used as sheathing systems for electrical or electronic cast systems or are used in epoxy or polyllrethslne foams. Thc reactioll resin compositions can be Iklui(l or p~llverulellt materi;lls.
Suitable epoxy resins are all types of epoxy resins, such as, for exarnple, those containing groups of formula / \
CH--C--CH
R' R" R"' that are bonded directly to oxygen, nitrogen or sulfur atoms, wherein either R' and R"' are each a hydrogen atom, in which case R" is a hydrogen atom or a methyl group, or R' and R"' together are -CH2CH2- or -C~I2CH2CH2-, in which case R" is a hydrogen atom.
Examples of such resins are polyglycidyl and poly(~-methylglycidyl) esters which can be obtained by reaction of a compound containing two or more carboxylic acid groups per molecule with epichlorohydrin, glycerol dichlorohydrin or ,~-methylepichlorohydrin in the presence of alkali. Such polyglycidyl esters can be derived from aliphatic polycarboxylic acids, for exalllple oxalic acid, succinic acid, glutaric acid, adipic acicl, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerised or trimerised linoleic acid, cycloaliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid and 4-methylhexahydrophthalic acid, and aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.
2~237~
Further examples are polyglycidyl and poly~ methylglycidyl) ethers which can be obtained by reaction of a compound containing at least two free alcoholic and/or phenolic hydroxy groups per molecule with the corresponding epichlorohydrin under alkaline conditions, or alternatively in the presence of an acidic catalyst with subsequent all~ali treatment. These ethers can be prepared with poly-(epichlorohydrin) from acyclicalcohols, such as ethylene glycol, diethylene glycol and higher poly-(oxyethylene) glycols, propane-1,2-diol and poly-(01cypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly-~oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolprop;me, pentaerythritol and sorbitol, from cycloaliphatic alcohols, sucll as resorcitol, quinitol, bis-(~-hydroxycyclollexyl)-lllethalle, 2,2-bis-t4-hydroxycyclohexyl)-propane nnd 1,1-bis-(hydroxymetllyl)-cyclohexene-3, ancl from nlcohols hnvillg aromntic nuclei, sllch as N,N-bis-(2-hydroxyetllyl)-nlliline ancl p,p'-bis-(2-hydloxyethylnmillo)-dipllellylmetllnlle~ They cnn nlso be prepnrecl ~roln mononuclenr phellols, such ns l~sorcinol nnd hy(lroq(lillolle, nnd polyllucleiar phellols, such as bis-(4-hydroxyphenyl)-methnne, 4,4-dihydroxydiphenyl, bis-(4-hydroxyphenyl)-sulfone, 1,1,2,2-tetralcis-(4-hydroxyphenyl)-ethane, '~,2-bis-(4-hydroxyphenyl)-propane (otherwise known as bisphenol A) and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-prop.me, and novolaks formed from aldehydes, such as formaldehyde, acetaldehyde, chloral and furfural, with phenols, such as phenol itself and phenol ring-substituted by chlorine atoms or by aLkyl groups each having up to nine carbon atoms, such as 4-chlorophenol, 2-methylphenol and 4-tert.-butylphenol.
Poly-(N-glycidyl) compounds include, for example, those obtained by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at leas~ two amino hydrogen atoms, such as aniline, n-butylamine, bis-~4-aminophenyl)-methane and bis-(4-methylaminophenyl)-methane, triglycidyl isocyanurate and N,N'-diglycidyl derivatives of cyclic alkyleneureas, such as ethyleneurea and 1,3-propyleneurea, and hydantoins, such as 5,5-dimethylhydantoin.
Poly-(S-glycidyl) compounds are, for example, the di-S-glycidyl der;vatives of dithiols, such as ethane-1,2-dithiol and bis-(4-mercaptomethylphenyl) ether.
Examples of epoxy resins having groups of formula - - 2~ 2~3 CH--C--CH
R' R" R"' wherein R' and R"' together are a -CH2CH2- group, are bis-(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1,2-bis-(2,3-epoxycyclopentyloxy)-ethane and 3,4-epoxycyclohexylmethyl-3 ' ,4'-epoxycyclohexanecarboxylate.
Al30 suitable are epoxy resins in which the 1,2-epoxy groups are bonded to hetero atoms of various kinds, for example the N,N,0-triglycidyl derivative of 4-aminophenol, the glycidyl ether/glycidyl ester of salicylic acid or p-hydroxybenzoic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin and 2-glycidylo~;y-1,3-bis-(5,5-dimethyl- 1 -glycidylllydalltoin-3-yl)prop.llle.
If desired it is also possible to use epoxy resin mixtllres Preferred epoxy resins are the polyglycidyl ethers, polyglycidyl esters and N,N'-di-glycidylhydantoins. Especially preferred resins are the polyglycidyl ethers of 2,2-bis-(4-hydroxyphenyl)-propane, bis-(4-hydroxyphenyl)-methane or of a novolak, formed from formaldehyde and a phenol that is unsubstituted or substituted by an alkyl group having from ] to 9 carbon atoms, having a 1,2-epoxy content exceeding 0.5 val/kg.
Suitable polyurethane reSiDS are, for example, those containing as main constituent polyfunctional isocvanates and/or polyurethane prepolymers. Also suitable here are both aromatic and alipha~ic, monocyclic and polycyclic, polyfunctional isocyanate compounds, such as, for example, hexane-1,6-diisocyanate, cyclohexane- 1,3-diisocyanate and isomers, 4,4'-dicyclohexylmethane-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl-isocyanate, 1,3-dimethylbenzene-~ s'-diisocyanate and isomers, 1-methylbenzene-2,4-diisocyanate and isomers, naphthalene-1,4-diisocyanate, diphenyl ether 4,4'-diiso-cyanate and isomers, diphenylsulfone-4,4-diisocyanate and isomers, and tri~unctional and higher-function.sl isocyanates, such as, for example, 3,3',4,4'-diphenylmethanetetraiso-cyanate. It is also possible to use isocyanates that are masked in customary manner with phenol, cresol or caprolactam. Dimers and trimers of the mentioned polyvalent iso-cyanates can also be used. Such polyisocyanates have terminal free isocyanate groups and contain one or more uretodione and/or isocyanurate rings. Processes for the preparation of various liinds of such trimers and uretodiones are described, for example, in US Patent 2~ 23~3 Specifications 3 494 888, 3 108 100 and 2 977 370.
Examples of other polyisocyanates that can be used are toluylene-diisocyanate ordiphenylmethane-diisocyanate. Industrial diphenylmethane-diisocyannte having a content of higher-functional diisocyanates and a functionality with respect to isocyanate groups of more than 2 is especially suitable. .'~ furtller suitable aliphntic diisocyanate is xylylene-diisocyanate. Furthermore, a large number of aliphatic isocyanates having a functionality of 2 and above can be used.
In accordance with a further embodiment, polyurethane prepolymers ~re used instend of the polyfilnctional isocyannte compounds. Prepolymers should here be understood as being the adducts of an excess of yolyf~mctional isocyanates with polyfilnctionnl alcohols, for exmnple the reactioll proclllcts of one of the afore-mclltioned slromatic or nlipllalic diisocyallates with ethylelle glycol, propylelle glycol, glycerol, trimethylolplop.lllc or pent.lerytllritol. It is also possible to use as yrepolymers reactioll products of (liiso-cyanates with polyether polyols, for example polyether polyols based on polyethylene oxide or based on polypropylene oxide. Polyurethane prepolymers based on polyether polyols having molecular weights of from 200 to 10,000, especially from 500 to 3,000, are preferred. A large number of such polyether polyols is known to the person skilled in the field of polyurethanes; they are available from numerous manufacturers and are character-ised by their molecular weight (number average) which can be calculated from end group analyses. Other suitable polyether polyols are polyether polyols based on polytetrahydro-furan.
Instead of polyether polyols it is also possible to use polyester polyols. Suitable polyester polyols are reaction products of polyfunctional acids with polyfunctional alcohols, for example polyesters based on aliphatic and/or aromatic dicarboxylic acids and polyfunctional alcohols having a functionality of from 2 to 4. It is therefore possible to use polyesters of adipic acid, sebacic acid, phthalic acid, hydrophthalic acid and/or trimellitic acid on the one h;uld and ethylene glycol, propylene glycol, neopentyl glycol, hexane glycol, glycerol and/or trimethylolprop.me on the other hand. Polyester polyols havillg a molecular weight (number average) of from 500 to 5,000, especially from 600 to 2,000, are particularly suitable. Other suitable polyester polyols are the reaction products of caprolactone with alcohols having a functionality of from 2 to 4, for example the addition product of 1 to 5 moles of caprolactone with 1 mole of ethylene glycol, propylene glycol, glycerol and/or trimethylolpropane.
2~2~
A further suitable class of polyfunctional alcohols is polybutadienols. These are oligomers based on butadiene and containing OH groups as end groups. In this case products having a molecular weight in the range of from 200 to 4,000, especially from 500 to 3,000, are suitable.
In the preparation of the polyurethane prepolymers, the ratio of OH groups of the ~lcohol component to isocyanate groups is important. It is generally *om 1:2 to 1:10. Relatively high excesses of isocyanate tend to produce low-viscosity polyurethane prepolymers, whereas lower isocyanate excesses produce highly viscous, generally only prep~r~tiolls just spreadable with a trowel.
It is Icnown to the person skillecl in the field of polyurethalles th.lt the cross-linl;illg dellsity alld thlls the hardness of the polyureth.llles incre,lses with the functioll.llity of tlle isocyanate component or the polyol. Reference is ma(le here to the general techllical literature, for example to the monograph by Saunders and Frisch, "Polyurethanes,Chemistry and Technology, Vol. XVI of the High Polymers series "Interscience Publishers", New York/London, Part I (1962) and Part II (1964).
The reaction resin compositions according to the invention can be prepared in customary manner with the aid of known mixing apparatus (for example extruders, mixers, kneaders, cylinder mills, mills~.
Processing to form shaped articles of all kinds can be effected by customary processes with curing. Processing by the casting method or by the vacuum casting method isespecially suitable.
First of all, three master batches are prepared which are used in different amounts.
Master batch 1:
60 g of Sandoflam(~)5060 (by Sandoz Huningue, France) of formula \C/ 2 ~ / 2~ ~CH3 2~12~
are mixed together intensively with 100 g of an unmodified epoxy resin that is liquid at room temperature and is based on bisphenol .A and epichlorohydrin with an epoxy contcnt of from 5.25 to 5.40 equiv./kg, in a cylinder mill (type DH-3 by Drais, Gerrnany), to fom a master batch.
Master batch 2:
60 g of Sandoflam~5080 (by Sandoz Huningue, France) of forrnula \C/ 2 \ / 2\ ~C~3 CH3 C~20 O OCH2 C~13 are mixed toge~her intensively with 100 g of an unmodified epoxy resin that is liquid at room temperature and is based on bisphenol A and epichlorohydrin with an epoxy content of from 5.25 to 5.40 equiv./kg, in a cylinder mill (type DH-3 by Drais, Germany), to forrn a master batch.
Master batch 3:
10 g of the thixotropic agent Silica R 202 (by Degussa, Germany~ are mixed together intensively with 90 g of an unmodified epoxy resin that is liquid at room temperature and is based on bisphenol A and epichlorohydrin with an epoxy content of from 5.25 to 5.40 equiv./kg, in a cylinder mill (type DH-3 by Drais~ Germany), to form a master batch.
Example 1: 61.3 g of master batch 1 (containing 23 g of Sandoflarn(~5060 and 38.3 g of epoxy resin~ and 177 g of aluminium hydroxide (Apyral(~2 by Vereinigte Aluminiumwerke A~, Germany) are homogenised with 61.7 g of an unmodified epoxy resin that is liquid at room temperature and is based on bisphenol A and epichlorohydrin h.aving nn epoxy content of from 5.25 to 5.40 equiv./kg, by means of a dissolver mixer.
Tllis flame-retarded resin material is degassed ~n vacuo (about 15 minu$es at p = 5 mbar/pump output about 40 Vmin; temperature of the resin material T = 80C).
This resin material is mixed intensively with 90 g of a low- viscosity anhydride hardener - 2~ ~ 2~7~
based on methyltetrahydrophthalic acid anhydride using a paddle stirrer. This flame-retarded reaction resin material is degassed in vacuo (about lS minutes at p = i mbar/pump output about 40 I/min; temperature of the material T = gOC)~ It is then poured into 1.6 mm or 3.2 mm preheated plate molllds. Hardening takes place for l hour at 100C and for 3 hours at 120C.
Example 2: Analogously to the method used in Example 1 there are used:
41.3 g of master batch 1 74.3 g of epoxy resin 119.0 g of aluminium hydroxide (Apyral(~2) After evacu;ltion of this resin materi;ll in accordallce with Example 1, 30.0 g o~ a low-viscosity, cyclonliph;ltic polyatl~ e hard~ller ~ased on 3,3'-~litnethyl-4,4'-dintnino-dicyclohexylmct}l.llle are a(lded.
This flame-retarded reaction resin material is degassed in vacuo (about 15 minutes at p = 5 mbarfpllmp output about 4Q Umin; temperature of the material T = 60C). It is then poured into 1.6 mm or 3.2 mm preheated plate moulds. Hardening takes place for 1 hour at 60C and for 2 hours at 120C.
Example 3: Analogously to the method used in Example 1 there are used:
61.3 g of master batch 2 3û.0 g of master batch 3 34.7 g of epoxy resin 177.0 g of aluminium hydroxide (Apyral(~)2) After evacuation of this resin material in accordance with Example 1, 90.0 g of a low-viscosity anhydride hardener based on methyltetrahydrophthalic acid anhydride are added and mixed intensively using a paddle stirrer.
This flame-retarded reaction resin material is degassed in vacuo (about 15 minutes at p = 5 mbar/pump output about 40 Vmin; temperature of the material T = 80C). It is then po- red into 3.2 mm preheated plate moulds. Hardening takes place for 1 hour at 100C
and for 3 hours at 1 20C.
2~237~
Example 4: After removal from the moulds, the testpieces of Examples 1 to 3 are tested for combustibility in accordance with the standard of Underwriters Laboratories Inc. UL
94, 3rd Edition (Revised) dated 25th September, 1981 (horizontal combustibility test).
Three testpieces 127 x 12.7 x 1.6 mm in size are used as samples.
In addition, the glass transition temperature is determined by means of the DSC method (Differential Scanning Calorimetry).
The results are given in Table 1.
Table 1:
~ ~, ~ ~ .. ,.. . _ . , _ __ .
Example Flame-retardation according to UL for 1.6 mm HB HB HB
Flame-retarda~ion according to UL for 3.2 mm V-O V-O V-O
Glass transition temperature Tg [C] 124 118 125 Total filter content [% by weight] 51.00 49.20 51.60 Al(OH) content [% by weight] 45.G0 43.50 45.00 P content [Yo by weight]1.05 1.02 1.05 Example 5: 100 g of a trifunctional polyether polyol (Baygal~K55 by Bayer AG, Germany) are "dewatered" for about 90 minutes at a temperature of 110C and thenevacuated until free of bubbles (5 mbar, 5 minutes~. After cooling, 180 g of aluminium hydroxide (Apyral(~2 by Vereinigte Aluminiumwerke AG, Germany) and 20 g of --- 2~12~ 13 Sandoflam(~)5060 (Sandoz Huningue, France) are introduced with intensive stirring and the resulting resin material is evacuated (about 10 minutes at p = 5 mbar/pump output about 40 llmin.; temperature of the material T = 40C).
The resulting filled resin component is mixed intensively with the hardener, 25 g of methane-diphenyldiisocyanate (Baymidur(~'K88 by Bayer AG, Germany) and evacuated(about 10 minutes at p = 5 mbar/pump output about 40 Vmin~; temperature of the material T = 40C).
The resulting reaction resin material is then poured into 3 mm plate moulds (mould temperature about 20C) and cured for 15 hnurs at 40C.
After removal from the MOUIdS, the testpieces ~re tested for combustibility in accor(l;lllce with the Limiting Oxygen Inde:~ (ASTM 2683-77).
Result: Limiting-Oxygen-Index: 30.2
K-17510/-~/CGW 19 Fhlme-retarded reaction resin compositions The present invention relates to flame-retarded reaction resin compositions containing a mixture of a metal hydroxide and an organophs)sphorus compound, and to the use of such mixtures for the flame-retardation of reaction resin compositions~
US-A-4 220 472 discloses dioxaphospl~ alle oxides as flame-proofing agents for polymers, especially for cellulose. ~lso, US-A-4 219 607 describes lligh-voltageinsulating matcrials that contaill ml additive that prevents trackillg and a phosphoms-cont;linillg compolllld as erosion islhibitor. Furthermore, US-A-4 668 7 l 8 discloses self-extit!guisllillg, track-resistal~t epo.~y resin mouldillg materials that contain aluminium hydroxide and calcium phosphate as flame-retardant components.
The flame-resistance of reaction resin materials is generally improved by reducing the proportion of organic, and therefore combustible, material, that is to say by the addition of non-combustible or difficultly combustible fillers, such as quartz powder, glass, wollastonite etc. In order to achieve adequate flame-protection, however, the proportion of filler must be very high, which often results in insoluble problems in the manufacture and processing of the reaction resin materials.
A further possibility is the addition of flame-proofing agents to the reaction resin materials. Inorganic additives, such as, for example, boron compounds or metal hydroxides, are suitable. In this case too, large proportions of such additives are necessary, which also has an adverse effect on manufacture and processing. The use of halogenated compounds, such as, for example, brominated bisphenol A epoxy resins or brominated anhydride hardeners, of which the flame-retardant action is generally assisted by a synergistic agent, for ex~m1ple Sb203, has the serious disadvantage that hydrogen halide is released on burning. Not only is hydrogen halide hazardous from a toxicological standpoint but it has an extremely high corrosion potential, which in the event of a -fire in an electrical unit, ~specially an electronic unit, could result in serious secondary damage as a result of electrochemical corrosion.
2~2~7~
The use for flame-retardation purpos~s of organophosphorus compounds that are not incorporated in the reaction resin moulding material gives rise to a form of plasticiser effect, which results in considerable loss of mechanical and electrical properties in the reaction resin moulding materials that have undergone such flame-retardant treatment. For example, the strength parnmeters and/or the glass transition temperature are reduced as a result of the plasticising effect of the organophosphorus coMpound. In addition, those compounds are generally unstable to hydrolysis, which results in the reaction resin moulding material exhibiting increased water absorption with the simultaneous fo~mation of various phosphoric acid compounds.
Surprisingly, there has now been discovered a flame-ret,lrdallt mi:cture for use in reactio resin materials that does not impair their processability and that brings about an increase in the flame-resistance of the Mouldillg m;lterials but does not h.lve illl adverse effect on their properties, sllch as therm;ll stability, tllCCh.llliC.II sLrength or water absorp~ioll The present invention relates to reaction resin compositions containing as flame-retardant a mixture of a) a hydroxide cf a metal of group 2 or 13 of the Periodic Table of Elements, and b) an organophosphorus compound of general forrnula I
R4 Rs 4 / 5 `C/ O X X O `C R
\1111/ \~ 1 R2 \CH 0/\0--C/H R2 (I), wherein X each independently of the other is oxygen or sulfur, Rl each independently of the other is hydrogen, an alkyl radical having from l to 4 carbon atoms or phenyl, R2 each independently of the other is hydrogen or an nlkyl radical having from 1 to 4 carbon atoms, or l and R~ together with the common carbon atom form a cyclohexylidene or cyclohexenylidene ring, 3 and R5 are each independently hydrogen or an alkyl radical having from 1 to 4 carbon atoms, and 2~2~
R4 each independently of the other is hydrogen or methyl, wherein at least one of the substituents R~ 2, R3, R4 and Rs is other than hydrogen, and when Rl and R2 form a ring together with the common carbon atom, R3, R4 and Rs are always hydrogen.
When Rl, R2, R3 or Rs is an allcyl radical having from 1 to 4 carbon atoms, that radical can be branched or straight-chain and is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl or tert.-butyl, but p~eferably methyl or ethyl, especially methyl.
Preferred compounds of formula I are those wherein each of Rl and R2, independently of the other, is hydrogen or alkyl having from 1 to 4 c,lrbon ntoms, or Rl and R2 together with thc common carbon atom form a cyclohexylidelle or cyclohexellylidene ring and R3, R~l and Rs are eacll hydrogen Compounds of formula I wherein Rl ~ld R2 are each alkyl having from 1 to 4 c~rbon atoms, especially methyl, are especially preferred Compounds of formula I that are very especially preferred are bis-(2-thiono-5,5-dimethyl-1,3,2-dioxaphosphinan-2-yl)-oxide and bis-(2-oxo-5 ,5-dimethyl- 1 ,3,2-dioxaphosphinan-2-yl)-oxide.
The designation of the groups in the Periodic Table of Elements corresponds to the new notation, as described in Chem. and Eng. News 63(5), 27, (1985).
The metal hydroxides suitable as component a) of the flame-retardant mixture are, for example, magnesium hydroxide, calcium hydroxide, boron hydroxide and aluminium hydroxide. Magnesium hydroxide and aluminium hydroxide or a mixture of the two hydroxides are preferred.
The preparation of components a) and b) of the flame-retardant rnixture is effected according to methods known ~ se. The metal hydroxides a) are mostly commerciallyavailable. The organophosphorus compounds can be prepared, for example, according tu the method described in US-A-4 220 472 and some of them are also commercially available.
2 ~ 3 The amounts of the individual components relative to the total weight of the reactioll resin compositions are advantageously, for component a), up to 70 % by weight, but preferably from 20 to 60 % by weight, especially from 30 to 50 % by weight; and for component b) from 2 to 40 % by weight, but preferably from 2 to 20 % by weight, especially from 5 to 15 % by weight. The content of components a) and b) together is a maximum of 85 % by weight, preferably 70 % by weight, relative to the total weight of the reaction resin compositions.
The mixture according to the invention is very suitable as a flame-retardallt for reaction resin materials. Especially suitable reaction resins nre epoxy rcsins ancl polyllrethane resins. The reaction resin compositions rendered llame-retardant according to the il~Vt~ll-tion are preferably used as sheathing systems for electrical or electronic cast systems or are used in epoxy or polyllrethslne foams. Thc reactioll resin compositions can be Iklui(l or p~llverulellt materi;lls.
Suitable epoxy resins are all types of epoxy resins, such as, for exarnple, those containing groups of formula / \
CH--C--CH
R' R" R"' that are bonded directly to oxygen, nitrogen or sulfur atoms, wherein either R' and R"' are each a hydrogen atom, in which case R" is a hydrogen atom or a methyl group, or R' and R"' together are -CH2CH2- or -C~I2CH2CH2-, in which case R" is a hydrogen atom.
Examples of such resins are polyglycidyl and poly(~-methylglycidyl) esters which can be obtained by reaction of a compound containing two or more carboxylic acid groups per molecule with epichlorohydrin, glycerol dichlorohydrin or ,~-methylepichlorohydrin in the presence of alkali. Such polyglycidyl esters can be derived from aliphatic polycarboxylic acids, for exalllple oxalic acid, succinic acid, glutaric acid, adipic acicl, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerised or trimerised linoleic acid, cycloaliphatic polycarboxylic acids, such as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid and 4-methylhexahydrophthalic acid, and aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.
2~237~
Further examples are polyglycidyl and poly~ methylglycidyl) ethers which can be obtained by reaction of a compound containing at least two free alcoholic and/or phenolic hydroxy groups per molecule with the corresponding epichlorohydrin under alkaline conditions, or alternatively in the presence of an acidic catalyst with subsequent all~ali treatment. These ethers can be prepared with poly-(epichlorohydrin) from acyclicalcohols, such as ethylene glycol, diethylene glycol and higher poly-(oxyethylene) glycols, propane-1,2-diol and poly-(01cypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly-~oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolprop;me, pentaerythritol and sorbitol, from cycloaliphatic alcohols, sucll as resorcitol, quinitol, bis-(~-hydroxycyclollexyl)-lllethalle, 2,2-bis-t4-hydroxycyclohexyl)-propane nnd 1,1-bis-(hydroxymetllyl)-cyclohexene-3, ancl from nlcohols hnvillg aromntic nuclei, sllch as N,N-bis-(2-hydroxyetllyl)-nlliline ancl p,p'-bis-(2-hydloxyethylnmillo)-dipllellylmetllnlle~ They cnn nlso be prepnrecl ~roln mononuclenr phellols, such ns l~sorcinol nnd hy(lroq(lillolle, nnd polyllucleiar phellols, such as bis-(4-hydroxyphenyl)-methnne, 4,4-dihydroxydiphenyl, bis-(4-hydroxyphenyl)-sulfone, 1,1,2,2-tetralcis-(4-hydroxyphenyl)-ethane, '~,2-bis-(4-hydroxyphenyl)-propane (otherwise known as bisphenol A) and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-prop.me, and novolaks formed from aldehydes, such as formaldehyde, acetaldehyde, chloral and furfural, with phenols, such as phenol itself and phenol ring-substituted by chlorine atoms or by aLkyl groups each having up to nine carbon atoms, such as 4-chlorophenol, 2-methylphenol and 4-tert.-butylphenol.
Poly-(N-glycidyl) compounds include, for example, those obtained by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at leas~ two amino hydrogen atoms, such as aniline, n-butylamine, bis-~4-aminophenyl)-methane and bis-(4-methylaminophenyl)-methane, triglycidyl isocyanurate and N,N'-diglycidyl derivatives of cyclic alkyleneureas, such as ethyleneurea and 1,3-propyleneurea, and hydantoins, such as 5,5-dimethylhydantoin.
Poly-(S-glycidyl) compounds are, for example, the di-S-glycidyl der;vatives of dithiols, such as ethane-1,2-dithiol and bis-(4-mercaptomethylphenyl) ether.
Examples of epoxy resins having groups of formula - - 2~ 2~3 CH--C--CH
R' R" R"' wherein R' and R"' together are a -CH2CH2- group, are bis-(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1,2-bis-(2,3-epoxycyclopentyloxy)-ethane and 3,4-epoxycyclohexylmethyl-3 ' ,4'-epoxycyclohexanecarboxylate.
Al30 suitable are epoxy resins in which the 1,2-epoxy groups are bonded to hetero atoms of various kinds, for example the N,N,0-triglycidyl derivative of 4-aminophenol, the glycidyl ether/glycidyl ester of salicylic acid or p-hydroxybenzoic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin and 2-glycidylo~;y-1,3-bis-(5,5-dimethyl- 1 -glycidylllydalltoin-3-yl)prop.llle.
If desired it is also possible to use epoxy resin mixtllres Preferred epoxy resins are the polyglycidyl ethers, polyglycidyl esters and N,N'-di-glycidylhydantoins. Especially preferred resins are the polyglycidyl ethers of 2,2-bis-(4-hydroxyphenyl)-propane, bis-(4-hydroxyphenyl)-methane or of a novolak, formed from formaldehyde and a phenol that is unsubstituted or substituted by an alkyl group having from ] to 9 carbon atoms, having a 1,2-epoxy content exceeding 0.5 val/kg.
Suitable polyurethane reSiDS are, for example, those containing as main constituent polyfunctional isocvanates and/or polyurethane prepolymers. Also suitable here are both aromatic and alipha~ic, monocyclic and polycyclic, polyfunctional isocyanate compounds, such as, for example, hexane-1,6-diisocyanate, cyclohexane- 1,3-diisocyanate and isomers, 4,4'-dicyclohexylmethane-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl-isocyanate, 1,3-dimethylbenzene-~ s'-diisocyanate and isomers, 1-methylbenzene-2,4-diisocyanate and isomers, naphthalene-1,4-diisocyanate, diphenyl ether 4,4'-diiso-cyanate and isomers, diphenylsulfone-4,4-diisocyanate and isomers, and tri~unctional and higher-function.sl isocyanates, such as, for example, 3,3',4,4'-diphenylmethanetetraiso-cyanate. It is also possible to use isocyanates that are masked in customary manner with phenol, cresol or caprolactam. Dimers and trimers of the mentioned polyvalent iso-cyanates can also be used. Such polyisocyanates have terminal free isocyanate groups and contain one or more uretodione and/or isocyanurate rings. Processes for the preparation of various liinds of such trimers and uretodiones are described, for example, in US Patent 2~ 23~3 Specifications 3 494 888, 3 108 100 and 2 977 370.
Examples of other polyisocyanates that can be used are toluylene-diisocyanate ordiphenylmethane-diisocyanate. Industrial diphenylmethane-diisocyannte having a content of higher-functional diisocyanates and a functionality with respect to isocyanate groups of more than 2 is especially suitable. .'~ furtller suitable aliphntic diisocyanate is xylylene-diisocyanate. Furthermore, a large number of aliphatic isocyanates having a functionality of 2 and above can be used.
In accordance with a further embodiment, polyurethane prepolymers ~re used instend of the polyfilnctional isocyannte compounds. Prepolymers should here be understood as being the adducts of an excess of yolyf~mctional isocyanates with polyfilnctionnl alcohols, for exmnple the reactioll proclllcts of one of the afore-mclltioned slromatic or nlipllalic diisocyallates with ethylelle glycol, propylelle glycol, glycerol, trimethylolplop.lllc or pent.lerytllritol. It is also possible to use as yrepolymers reactioll products of (liiso-cyanates with polyether polyols, for example polyether polyols based on polyethylene oxide or based on polypropylene oxide. Polyurethane prepolymers based on polyether polyols having molecular weights of from 200 to 10,000, especially from 500 to 3,000, are preferred. A large number of such polyether polyols is known to the person skilled in the field of polyurethanes; they are available from numerous manufacturers and are character-ised by their molecular weight (number average) which can be calculated from end group analyses. Other suitable polyether polyols are polyether polyols based on polytetrahydro-furan.
Instead of polyether polyols it is also possible to use polyester polyols. Suitable polyester polyols are reaction products of polyfunctional acids with polyfunctional alcohols, for example polyesters based on aliphatic and/or aromatic dicarboxylic acids and polyfunctional alcohols having a functionality of from 2 to 4. It is therefore possible to use polyesters of adipic acid, sebacic acid, phthalic acid, hydrophthalic acid and/or trimellitic acid on the one h;uld and ethylene glycol, propylene glycol, neopentyl glycol, hexane glycol, glycerol and/or trimethylolprop.me on the other hand. Polyester polyols havillg a molecular weight (number average) of from 500 to 5,000, especially from 600 to 2,000, are particularly suitable. Other suitable polyester polyols are the reaction products of caprolactone with alcohols having a functionality of from 2 to 4, for example the addition product of 1 to 5 moles of caprolactone with 1 mole of ethylene glycol, propylene glycol, glycerol and/or trimethylolpropane.
2~2~
A further suitable class of polyfunctional alcohols is polybutadienols. These are oligomers based on butadiene and containing OH groups as end groups. In this case products having a molecular weight in the range of from 200 to 4,000, especially from 500 to 3,000, are suitable.
In the preparation of the polyurethane prepolymers, the ratio of OH groups of the ~lcohol component to isocyanate groups is important. It is generally *om 1:2 to 1:10. Relatively high excesses of isocyanate tend to produce low-viscosity polyurethane prepolymers, whereas lower isocyanate excesses produce highly viscous, generally only prep~r~tiolls just spreadable with a trowel.
It is Icnown to the person skillecl in the field of polyurethalles th.lt the cross-linl;illg dellsity alld thlls the hardness of the polyureth.llles incre,lses with the functioll.llity of tlle isocyanate component or the polyol. Reference is ma(le here to the general techllical literature, for example to the monograph by Saunders and Frisch, "Polyurethanes,Chemistry and Technology, Vol. XVI of the High Polymers series "Interscience Publishers", New York/London, Part I (1962) and Part II (1964).
The reaction resin compositions according to the invention can be prepared in customary manner with the aid of known mixing apparatus (for example extruders, mixers, kneaders, cylinder mills, mills~.
Processing to form shaped articles of all kinds can be effected by customary processes with curing. Processing by the casting method or by the vacuum casting method isespecially suitable.
First of all, three master batches are prepared which are used in different amounts.
Master batch 1:
60 g of Sandoflam(~)5060 (by Sandoz Huningue, France) of formula \C/ 2 ~ / 2~ ~CH3 2~12~
are mixed together intensively with 100 g of an unmodified epoxy resin that is liquid at room temperature and is based on bisphenol .A and epichlorohydrin with an epoxy contcnt of from 5.25 to 5.40 equiv./kg, in a cylinder mill (type DH-3 by Drais, Gerrnany), to fom a master batch.
Master batch 2:
60 g of Sandoflam~5080 (by Sandoz Huningue, France) of forrnula \C/ 2 \ / 2\ ~C~3 CH3 C~20 O OCH2 C~13 are mixed toge~her intensively with 100 g of an unmodified epoxy resin that is liquid at room temperature and is based on bisphenol A and epichlorohydrin with an epoxy content of from 5.25 to 5.40 equiv./kg, in a cylinder mill (type DH-3 by Drais, Germany), to forrn a master batch.
Master batch 3:
10 g of the thixotropic agent Silica R 202 (by Degussa, Germany~ are mixed together intensively with 90 g of an unmodified epoxy resin that is liquid at room temperature and is based on bisphenol A and epichlorohydrin with an epoxy content of from 5.25 to 5.40 equiv./kg, in a cylinder mill (type DH-3 by Drais~ Germany), to form a master batch.
Example 1: 61.3 g of master batch 1 (containing 23 g of Sandoflarn(~5060 and 38.3 g of epoxy resin~ and 177 g of aluminium hydroxide (Apyral(~2 by Vereinigte Aluminiumwerke A~, Germany) are homogenised with 61.7 g of an unmodified epoxy resin that is liquid at room temperature and is based on bisphenol A and epichlorohydrin h.aving nn epoxy content of from 5.25 to 5.40 equiv./kg, by means of a dissolver mixer.
Tllis flame-retarded resin material is degassed ~n vacuo (about 15 minu$es at p = 5 mbar/pump output about 40 Vmin; temperature of the resin material T = 80C).
This resin material is mixed intensively with 90 g of a low- viscosity anhydride hardener - 2~ ~ 2~7~
based on methyltetrahydrophthalic acid anhydride using a paddle stirrer. This flame-retarded reaction resin material is degassed in vacuo (about lS minutes at p = i mbar/pump output about 40 I/min; temperature of the material T = gOC)~ It is then poured into 1.6 mm or 3.2 mm preheated plate molllds. Hardening takes place for l hour at 100C and for 3 hours at 120C.
Example 2: Analogously to the method used in Example 1 there are used:
41.3 g of master batch 1 74.3 g of epoxy resin 119.0 g of aluminium hydroxide (Apyral(~2) After evacu;ltion of this resin materi;ll in accordallce with Example 1, 30.0 g o~ a low-viscosity, cyclonliph;ltic polyatl~ e hard~ller ~ased on 3,3'-~litnethyl-4,4'-dintnino-dicyclohexylmct}l.llle are a(lded.
This flame-retarded reaction resin material is degassed in vacuo (about 15 minutes at p = 5 mbarfpllmp output about 4Q Umin; temperature of the material T = 60C). It is then poured into 1.6 mm or 3.2 mm preheated plate moulds. Hardening takes place for 1 hour at 60C and for 2 hours at 120C.
Example 3: Analogously to the method used in Example 1 there are used:
61.3 g of master batch 2 3û.0 g of master batch 3 34.7 g of epoxy resin 177.0 g of aluminium hydroxide (Apyral(~)2) After evacuation of this resin material in accordance with Example 1, 90.0 g of a low-viscosity anhydride hardener based on methyltetrahydrophthalic acid anhydride are added and mixed intensively using a paddle stirrer.
This flame-retarded reaction resin material is degassed in vacuo (about 15 minutes at p = 5 mbar/pump output about 40 Vmin; temperature of the material T = 80C). It is then po- red into 3.2 mm preheated plate moulds. Hardening takes place for 1 hour at 100C
and for 3 hours at 1 20C.
2~237~
Example 4: After removal from the moulds, the testpieces of Examples 1 to 3 are tested for combustibility in accordance with the standard of Underwriters Laboratories Inc. UL
94, 3rd Edition (Revised) dated 25th September, 1981 (horizontal combustibility test).
Three testpieces 127 x 12.7 x 1.6 mm in size are used as samples.
In addition, the glass transition temperature is determined by means of the DSC method (Differential Scanning Calorimetry).
The results are given in Table 1.
Table 1:
~ ~, ~ ~ .. ,.. . _ . , _ __ .
Example Flame-retardation according to UL for 1.6 mm HB HB HB
Flame-retarda~ion according to UL for 3.2 mm V-O V-O V-O
Glass transition temperature Tg [C] 124 118 125 Total filter content [% by weight] 51.00 49.20 51.60 Al(OH) content [% by weight] 45.G0 43.50 45.00 P content [Yo by weight]1.05 1.02 1.05 Example 5: 100 g of a trifunctional polyether polyol (Baygal~K55 by Bayer AG, Germany) are "dewatered" for about 90 minutes at a temperature of 110C and thenevacuated until free of bubbles (5 mbar, 5 minutes~. After cooling, 180 g of aluminium hydroxide (Apyral(~2 by Vereinigte Aluminiumwerke AG, Germany) and 20 g of --- 2~12~ 13 Sandoflam(~)5060 (Sandoz Huningue, France) are introduced with intensive stirring and the resulting resin material is evacuated (about 10 minutes at p = 5 mbar/pump output about 40 llmin.; temperature of the material T = 40C).
The resulting filled resin component is mixed intensively with the hardener, 25 g of methane-diphenyldiisocyanate (Baymidur(~'K88 by Bayer AG, Germany) and evacuated(about 10 minutes at p = 5 mbar/pump output about 40 Vmin~; temperature of the material T = 40C).
The resulting reaction resin material is then poured into 3 mm plate moulds (mould temperature about 20C) and cured for 15 hnurs at 40C.
After removal from the MOUIdS, the testpieces ~re tested for combustibility in accor(l;lllce with the Limiting Oxygen Inde:~ (ASTM 2683-77).
Result: Limiting-Oxygen-Index: 30.2
Claims (7)
1. A reaction resin composition containing as flame-retardant a mixture of a) a hydroxide of a metal of group 2 or 13 of the Periodic Table of Elements, and b) an organophosphorus compound of general formula I
(I), wherein X each independently of the other is oxygen or sulfur, R1 each independently of the other is hydrogen, an alkyl radical having from 1 to 4 carbon atoms or phenyl, R2 each independently of the other is hydrogen or an alkyl radical having from 1 to 4 carbon atoms, or R1 and R2 together with the common carbon atom form a cyclohexylidene or cyclohexenylidene ring, R3 and R5 are each independently hydrogen or an alkyl radical having from 1 to 4 carbon atoms, and R4 each independently of the other is hydrogen or methyl, wherein at least one of the substituents R1, R2, R3, R4 and R5 is other than hydrogen, and when R1 and R2 form a ring together with the common carbon atom, R3, R4 and R5 are always hydrogen.
(I), wherein X each independently of the other is oxygen or sulfur, R1 each independently of the other is hydrogen, an alkyl radical having from 1 to 4 carbon atoms or phenyl, R2 each independently of the other is hydrogen or an alkyl radical having from 1 to 4 carbon atoms, or R1 and R2 together with the common carbon atom form a cyclohexylidene or cyclohexenylidene ring, R3 and R5 are each independently hydrogen or an alkyl radical having from 1 to 4 carbon atoms, and R4 each independently of the other is hydrogen or methyl, wherein at least one of the substituents R1, R2, R3, R4 and R5 is other than hydrogen, and when R1 and R2 form a ring together with the common carbon atom, R3, R4 and R5 are always hydrogen.
2. A reaction resin composition according to claim 1, wherein the reaction resin is an epoxy resin or a polyurethane resin.
3. A reaction resin composition according to claim 1, wherein the metal in a) isaluminium or magnesium.
4. A reaction resin composition according to claim 1, wherein in the compound of for-mula I each of R1 and R2, independently of the other, is hydrogen or alkyl having from 1 to 4 carbon atoms, or R1 and R2 together with the common carbon atom form a cyclohexylidene or cyclohexenylidene ring and R3, R4 and R5 are each hydrogen.
5. A reaction resin composition according to claim 4, wherein in the compound of for-mula I R1 and R2 are each alkyl having from 1 to 4 carbon atoms.
6. A reaction resin composition according to claim 5, wherein in the compound of for-mula I R1 and R2 are methyl.
7. A process for the flame-retardation of reaction resin compositions, in which process a mixture of a) a metal hydroxide and b) an organophosphorus compound of general for-mula I according to claim 1 is incorporated into the reaction resin composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1063/89-9 | 1989-03-22 | ||
| CH106389 | 1989-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2012573A1 true CA2012573A1 (en) | 1990-09-22 |
Family
ID=4201587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002012573A Abandoned CA2012573A1 (en) | 1989-03-22 | 1990-03-20 | Flame-retarded reaction resin compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0389433A1 (en) |
| JP (1) | JPH02284987A (en) |
| KR (1) | KR900014564A (en) |
| CA (1) | CA2012573A1 (en) |
| DD (1) | DD298801A5 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8466096B2 (en) | 2007-04-26 | 2013-06-18 | Afton Chemical Corporation | 1,3,2-dioxaphosphorinane, 2-sulfide derivatives for use as anti-wear additives in lubricant compositions |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08239621A (en) * | 1995-03-07 | 1996-09-17 | Kiyapitaru Paint Kk | Flame-retardant clear coating material |
| CN102471535B (en) * | 2009-07-24 | 2013-12-11 | 巴斯夫欧洲公司 | Derivatives of diphosphines as flame retardants in aromatic and/or heteroaromatic epoxy resins |
| JP5263116B2 (en) * | 2009-10-14 | 2013-08-14 | 東洋インキＳｃホールディングス株式会社 | Flame retardant resin composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH581163A5 (en) * | 1974-07-30 | 1976-10-29 | Sandoz Ag | |
| US4668718A (en) * | 1984-10-05 | 1987-05-26 | Ciba-Geigy Corporation | Self-extinguishing, track-resistant epoxy resin moulding composition and use thereof |
-
1990
- 1990-03-14 EP EP90810203A patent/EP0389433A1/en not_active Withdrawn
- 1990-03-20 DD DD90338910A patent/DD298801A5/en not_active IP Right Cessation
- 1990-03-20 CA CA002012573A patent/CA2012573A1/en not_active Abandoned
- 1990-03-22 JP JP2073180A patent/JPH02284987A/en active Pending
- 1990-03-22 KR KR1019900003966A patent/KR900014564A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8466096B2 (en) | 2007-04-26 | 2013-06-18 | Afton Chemical Corporation | 1,3,2-dioxaphosphorinane, 2-sulfide derivatives for use as anti-wear additives in lubricant compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| DD298801A5 (en) | 1992-03-12 |
| EP0389433A1 (en) | 1990-09-26 |
| JPH02284987A (en) | 1990-11-22 |
| KR900014564A (en) | 1990-10-24 |
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