JPS6019327B2 - Flame-resistant and optionally self-extinguishing polyamide, polyolefin, polyacrylate or epoxy compositions - Google Patents

Description

[Detailed description of the invention]

Methods for producing key-flame fibers and other polymeric compositions are already known in a wide variety of ways. Regarding the numerous developments in this field, mention may be made, for example, of the following references: Hans Vogel (n.s.
"Flammfestmächen Von Kunstschutsfuen" (Flammfestmachen)
vonKunsPtoffen)”, Dr. Alfred Huthig Publishers (Dr.NfredHuth
ig, Verlag), Heidelberg, 1966; John W. Lyons.
Author: “The Chemistry and Uses of Fire Retardants”
Uses of Fire Retardants)
”, Wiley-Int.
King Alec William (AIlec), New York, London, Toronto, 197th King;
Willjam), “FlameResistant Fabrics”
s)'', Noyes Data Co.
poration), Park Ridge, New Jersey, London, 197 Phantom King. Periodical “Textilveredrun”
g) ''Volume 10, No. 1, published in May 1975
Known commercial flame retardants mostly contain the elements phosphorus, halogens and nitrogen. In most cases, antimony is also added to the flame retardant in order to increase the flame retardant effect. For example, added in the form of Sb203,
Therefore, flame-retardant polymers generally contain relatively high percentages of additives. Incorporation of this amount and quality of fire retardant treatments into polymers is associated with a number of adverse effects. When added in effective amounts, flame retardants of this type adversely affect at least one of the physical and use properties of the polymer. For example, they generally cause significant deterioration in flexural strength, elongation, initial modulus, modulus of elasticity, and poor color. Furthermore, especially in the case of threads, only an unsatisfactory flameproofing effect is often achieved despite the relatively high amount of flameproofing agent in the polymer, and therefore the extremes of flameproofing of polymers treated in this way are Only some of them have self-extinguishing properties. The known flame retardants of the state of the art are mostly and mostly harmful to the skin. For example, many bromine-containing compounds cause dermatitis.
Furthermore, many phosphorus compounds, especially halogenated phosphate esters, are highly toxic. The flame retardants of the state of the art, which decompose during the combustion process, also contain toxic and sometimes toxic gases, such as hydrohalic acids, elemental halogens, halogen-oxygen compounds, nitrogen oxides, nitrogen-hydrogen compounds, and in some cases their Generates hydrogen cyanide and dicyanide. In the case of composites, a further series of known flame retardants promote the decomposition of polymer melts during combustion. This increases the dripping of the partially combustible polymer melt. When flame retardants are used in yarns and fibers, common commercially available products only exhibit a temporary flame retardant effect because they are denatured by multiple washings or dry cleanings. be. Commercially available flame retardants, especially bromine-containing products, are relatively expensive.
For many flame retardants of this type, special techniques, e.g. mixers, special dosing methods via dosing pumps, have to be developed in order to further incorporate the bromine into the polymer. The chemical aggressiveness of the compounds causes corrosion problems. Surprisingly, it has now been found that rust compounds of oxalic acid are superior flame retardants for polyamides, polyolefins, polyacrylates and epoxy resins compared to simple salts of oxalic acid. The use of Oxalato resin has hitherto been carried out only in special cases and in practice exclusively in connection with the flameproofing of polyamides by post-treatment with solutions of flameproofing agents. According to the method for flameproofing a filled polyamide molding material or a bulk graft polymer described in German Patent Application No. 194118, strongly brominated polyether and antimony trioxide or A mixture of asothymonyl compounds is used. Examples of antimonyl compounds include antimony hydroxide (
In addition to sodium antimonite, antimony chloride and antimony potassium tartrate, mention may also be made of antimony oxalate in the rust form, such as NaSb(C204)2. The oxalato complex in this case is only one of the possible antimony carriers. This publication makes no mention of the obvious flame-retardant effect of oxalic acid together. West German Patent Application Publication No. 2,152,1
From No. 96, a method is known for improving the flame resistance of natural and synthetic polyamide fibers using titanium-brim compounds, in which case the brim bodies are formed with organic chelating agents or fluoride ions. Here too, citric and tartaric bodies are preferred, although oxalato bodies are only mentioned as one of the possible heavy metal carriers. Flame retardants are generally applied to the textile material to be processed in the form of droplets. This method is particularly advantageous for wool and mixtures of wool and synthetic fibers, in which case the flame retardant should likewise be applied from the treatment liquid. This method works if all synthetic fibers are used.
This is of course not suitable, especially in the case of flameproofing of hydrophobic polyamides. In the case of mixtures of wool and fully synthetic fibers, only the wool component is of course flameproofed. Therefore, this specification also does not mention the use of oxalate compounds as flame retardants for polyamides, polyolefins, polyacrylates and epoxy resins. The same thing as mentioned above is stated in West German National Technical Patent Application Publication No. 2,212,71.
8, in which natural and synthetic polyamide fibers are treated with anionic compounds of zirconium and organic chelate formers or fluoride ions from an aqueous solution in the pH range of 0.5 to 4. be done. In this case too, oxalato rust bodies are mentioned as one of the possible carriers for zircon in addition to purely inorganic compounds, and no method is mentioned for fully synthetic fibers.
The object of the present invention is a permanently flame-resistant and optionally self-extinguishing composition of polyamides, polyolefins, polyphacrylates and epoxy resins, which compositions are used as one or more flame-resistant processing additives. It is characterized by homogeneously containing oxalato tsuba bodies. Oxalato rust bodies are particularly suitable for the formula: [Z(C204)n]-e, where Z is one or more central atoms, n is the number of ligands, and 1e is the negative chain anion. Examples include those containing a tsuba anion (representing electric charge). This kind of Oxalato coin body is known as K. V. Krishnamurti and G. M. Harris (Mrs.), “Chemical Reviews (ChemiaIR)
61 (1961), No. 213~
It is described in detail on page 246. The number of ligands is generally 1, 2, 3 or 4, and the charge of the complex anion is -1, -
2, 13, 14 or -5 and the number of the central atom is 1, in which case the number of ligands and the charge of the collar anion are determined by the coordination number and the charge of the central atom. Within the scope of the present invention, oxalato rust bodies with complex anions of the [Z(C204)n]-e type are understood not only to be compounds whose composition is precisely stoichiometric, but also to compounds with n and -e complexes. Compounds whose values deviate above or below integer numbers should also be understood. This occurs, for example, when a small portion of the oxalato ligand is converted by another ligand. Compounds of this type are formed during or after the synthesis of the oxalato complex by introducing or converting a foreign ligand into the complex anion. The same applies correspondingly to the central atom, ie also oxalato key bodies in which the cationic constituents are not strongly schematically combined are also included within the scope of the invention. That is, in this case as well, the value regarding the central atom may deviate from an integer. This means that
It occurs when a part of the central atom is replaced by another central atom having a different coordination number or valence. Deviations from exact stoichiometry of this type occur frequently in complex chemistry, as is well known, and are obvious to those skilled in the art. The oxalato bell bodies used in the present invention are also taught as mixed oxalato bell bodies containing, instead of stoichiometric amounts of central atoms, corresponding amounts of different central atoms. Of course, mixtures of various single or mixed oxalato complexes are also relevant. In particular, the central atom of the oxalato in preferred compounds with anion of the [Z(C204)n]-e type is metals: Mg, Ca, Sr,
Ship, Zr, Hf, Ce, V, Cr, Mn, Fe, Co,
Ni, Cu Zn, Cd, B, AI, Ga, ln, Sn
, Pb and Sb. The cationic components of the oxalato rust body are preferably ions: Li, Na, K, Rb, C
at least one of s or NH4 or the mother ion and the above ion
Includes one. General formula: Me army Me grass [Z (C204)
m] (1) [In the formula, Mel is Li, Na, K,
Rb, Cs or NH4, Me or one of the above cations or Ba, Z is the central atom: Mg, Ba,
Zr, Fe, Co, CrZn, AI, Sn, Cr and S
b and k = 0, 1, 2, 3 or 4, 1 = 0 or 1 and m = 22, 3 or 4] (said symbols are ,k,1
This indicates that the values of and m may deviate from integers. (See Examples 1 to 14). Particularly advantageous is the general formula: M
e31 [AI (C204) 3] or Mel [AI (C2
04)2] alkali aluminum-oxalato body and oxalato chain body: K4 [Zn(C204)3], &
[Zr(C204)4], K3[Cr(C204)3]
, K3[Fe(C204)3], K3[Sb(C204)
)3], KBa[C204)3], KBa[N(C20
4)3], K2[Mg(C204)2], K2[Fe(
C204)2]K2[Zn(C204)2], K2[C
u(C204)2], mother [Mg(C204)2]. Using the oxalate complexes described above, a new class of compounds has now been found which is highly suitable as flame retardants for polyamides, polyolefins, polyacrylates and epoxy resins. In general, cesium complexes have the best effectiveness, followed by rubidium, potassium, and sodium chains, and finally lithium complexes, which have relatively the lowest effectiveness. Mixed alkali metal/barium keys as well as barium/magnesium keys have a very good flameproofing effect. 1=0 and Z=AI

The compound of formula [1} is a lithium, sodium, potassium, rubidium, cesium, ammonium, aluminum dioxalate or aluminum trioxalate complex salt having a coordinatively tetravalent or hexavalent aluminum atom. It is. These are known and easily obtained, for example, by reacting aluminum sulfate with lithium oxalate, monosodium, -potassium, rubidium, monocesium or -ammonium solutions, and by precipitation from aqueous solutions of these components. Regarding the production method and properties of these fin salts, please refer to the ``Gmelins Handbutsuho der Anorganischen Chemie''.
dbuch der Amorganischen
Chemie)” 8th edition, “Aluminium”, Volume B 1
, Chemie GmbH Publishers, Wein/Im/Bergstrasse, 1933. Another method for producing potassium-aluminum trioxalate salt by treating freshly precipitated aluminum hydroxide with an aqueous solution of potassium hydrogen oxalate is called “Inorganic Synthesis”. Volume 1, McGraw-Hill Publishers (McG
rawHilIBookComp. ), Inc. New York and London, 1933, p. 36. Among the oxalato complexes with other central atoms,
Most of the compounds used in the present invention are likewise known and disclosed. This can be obtained by reacting the salt of the central atom with an alkali metal oxalate. Suitable compounds for the central atom include sulfates, chlorides,
hydroxide, acetate, carbonate and oxalate. Details of the preparation of these complexes can be found in the following document: D. P. Graddon, Kaoru, “Journal of Inorganic and Nuclear Chemistry (J.lno.g. & Nucl.C.
hem. )” 1956 King, Vol. 3, pp. 308-322, D. P. Gladdon, “Inorganic Syntheses”, Vol. 1, p. 36, K. V. Krishnamurti, “Chemical Reviews” 61 (1961)
, pp. 213-246. Oxalato anchors, the method of preparation of which is not explicitly described in the cited literature, can be prepared in a similar manner (see Examples below). Of course, in this case as well, the number of alkali metal and alkali metal atoms, that is, the magnitudes of k and ] and the magnitude of m, are determined by the valence of the central atom, and the present invention also provides that the composition is {1 It also includes the use of compounds that are not exactly stoichiometric in the sense of the formula, ie compounds in which the values of k, 1 and m deviate slightly above or below integers. The flame retardants according to the invention are particularly suitable for polyamides. Examples of polyamides include y-butyrolactone (nylon 4), 6-amino-hydroproic acid or docaprolactam (nylon 6), 7-aminophenanthoic acid (nylon 7), 11-amino-undecanoic acid ( Nylon 11),
Those based on 2-laurin lactam (nylon 12) and also those based on dibasic carboxylic acids and diamines, such as polyhexamethylene adipinamide (
Examples include nylon 66) and polyhexamethylene-sebacinamide (nylon 610), as well as aromatic polyamides such as poly p-penzamide, poly m-penzamide, and the like. Furthermore, oxalato rust bodies are suitable for use in particular with polyacrylates, such as polyacrylonitrile, polymethacrylate esters and polyacrylate esters and polyolefins,
For example, polyethylene, polypropylene, polybutylene,
Polyisoptylene, polystyrene, polyvinyl alcohol, polypinyl chloride, polypinylidene chloride are suitable as flame retardants for polyvinyl acetate and polypinyl ethers and epoxy resins. It is to be understood that eg modified polymers, copolymers and copolycondensates are also included.The flame retardant according to the invention is suitable for all customary molding materials of said polymers. These may be in the form of grains, pellets or strands, shaped bodies or yarns such as plates, sheets, films and fibres, textile products such as woven, knitted, fleece, canvas and carpets. Little is known about the mechanism and principle of action of Oxalato armor bodies used as agents. However, these compounds have been shown to slow combustion by intervening in the radical chain, e.g. by halogenated flame retardants. Thus, rather than intervening in the combustion process at one stage, the flame-retardant effect according to the invention is considered to be the result of multiple individual flame suppression processes at different stages of the combustion process. Flame retardants belong to the class of inert gas separating materials. They have the advantage of separating up to 4 moles of carbon dioxide per mole of starting material. Rather, the underlying principle of action is the following phenomenon: It is thought that: absorption of thermal energy from the melt by dissociation of flame retardant and heating of inert gas, CO2n separation during burning polymer combustion process by formation of oxide and salt layers, oxygen release at the surface of the melt. extrusion and dilution and promotion of the transfer of radical traps, e.g. alkali metal atoms, into the gas phase.Between the decomposition temperature and the effect of the flame retardant according to the invention on the one hand and the polymer to be flame-resistant processed on the other hand, It is clear that there are relationships that must be taken into account when choosing the oxalato complex. For example, the decomposition temperature below the melting temperature of the burning polymer is an important prerequisite for the effectiveness of the oxalato anchor. On the other hand, the oxalato rust body should be completely chemically inert up to the temperature at which molding takes place.A suitable oxalato rust body for polyhexamethylene adipamide is therefore a It should have a decomposition temperature above the processing temperature of xamethylene diadipamide, but not above the temperature of the burning polyhexamethylene diadipamide melt of about 49,000. If it is not mentioned in the literature,
It can be easily determined by thermogravimetric analysis (TGA). For TGA-implementation instructions, please refer to the
nnSEnCyclopadieder ni chnis
chenChemie)'' 3rd edition (1961), Urban & Schwalzenberg Verlag (Ver.
Listed in lagurn & schrzenrg), Munich-Berlin, volume 2/1, No. 65. The table below lists the decomposition temperatures of various oxalato complexes. The melting temperature of a combustible polymer, ie the temperature at which a combustible polymer melts in air, can be measured using, for example, a thermal cell. This measurement is advantageously carried out in such a way that the joints of the thermal cell are always covered with dripping melt during the measurement.
Examples of burning polymer temperatures include: Nylon 66: about 490°C; Berlon: about 400°C.
°C: Polyethylene: about 410oo. A very advantageous method for investigating the decomposition temperature is differential thermal analysis (DTA), since the position of the endothermic maximum in the DTA thermograph of the Oxalato body indicates the decomposition temperature. Regarding differential proficiency analysis, please refer to related references, such as “Urmans. Encyclopedia der Technischen.
Chemie", 1.c. 656th-65th Swordsman and Franke, "Lexicon der Ph$ik, Franckh'sche Verlasenhandl.
Skin g) Published in Stuttgart, 3rd edition.
When selecting a suitable oxalato base as a flame retardant for the polymer, it is advantageous to synchronize the decomposition temperature of the oxalato base and the melting temperature of the burning polymer as optimally as possible. A person skilled in the art attempts to make a very special polymer flame resistant,
If the DTA-value is not known and, moreover, the measurement of the melting temperature of the combustible polymer and the necessary equipment for the DTA-measurement are not provided, it can be determined by some experimentation which oxalate values are primarily relevant and Instantly find answers to questions about optimal fire protection. This also applies, of course, if, due to some unforeseen cause, it is not possible to achieve a satisfactory flame retardant effect even though the decomposition temperature of the oxalato rust and the melting temperature of the polymer are appropriate. That's true. The flame-resistant polymer obtained according to the present invention can be processed into conventional molded articles such as fibers, sheets, films, plates, injection molded articles, and the like. All complex salts according to the invention are excellent flame retardants. Particularly effective in the case of polyamide is Oxalato body: K2
[Mg(C204)2], Rb3[AI(C204)3
] and KBa[Fe(C204)3]. Compared to the usual complex salts, the latter two compounds in particular are distinguished by a sufficient prevention of dripping of the melt during combustion. The oxalic acid compounds used according to the invention have a pronounced flameproofing effect even in relatively small doses. They are advantageously used in amounts of 1 to 4% by weight, in particular 5 to 15% by weight, based on the flame-resistant and optionally self-extinguishing polymer. It is advantageous to use tsuba salt in water-free form. According to the invention, permanently flame-resistant and optionally self-extinguishing molding materials are produced by incorporating one or more oxalic acid salts according to the invention into polymeric substances in a customary manner. In this case, mention may be made, inter alia, of processes in which the flame retardant is added to the monomer already during the polyaddition, polymerization or polycondensation and is dispersed homogeneously in the polymer thus formed. Another possible compounding method is to melt the polymeric material, mix it with the flame retardant and subsequently process it into pellets or directly form it. The flame-resistant or self-extinguishing molding compound is suitable for use and can be selected without difficulty by those skilled in the art. Even if the shaped bodies are large or thick-walled, the distribution of the flame retardant takes place without problems, ie it is easy to prepare the flame retardant for this purpose in suitable particle sizes. In contrast, when producing flame-resistant or self-extinguishing fibers according to the method of the invention, in order to make the spinning of the polymer possible and to ensure good physical properties of the target product,
It is desirable to use flame retardants in very finely divided form. Again, the appropriate particle size will be determined based on the desired application and readily selected by one skilled in the art. For example, in the case of fibers, particle size depends on the fiber properties and the desired physical properties of the final product. In the case of fibers, tsuba salt with a particle size of up to about 2 mA can be used. The tsuba salt used in the present invention is easily pulverized. For example, it can be milled very easily, in which case adhering water and water of crystallization are removed beforehand. There is no problem in drying the tsuba salt, for example, it can be treated at 150 kg and 1 m Hg for several hours. Dry as well as wet milling may be performed. For wet milling, the selection of a suitable dispersion liquid will likewise be determined by the use and application of the flame retardant. When reinforcing the polymer with glass fibers, the flame retardant effect of the flame retardant of the present invention may be hindered to some extent in the case of glass fibers containing alkali metals, especially calcium. It should be kept in mind. This interference is attributed to the presence of alkali metals, such as calcium, encapsulated in the polymer via the glass fibers. Apparently, calcium in its oxide form reacts with the oxalato complex under melt conditions to form a rust body depleted of calcium oxalate and oxalato ligands. This reaction appears to result in gradual decomposition of the flame retardant within the melt such that only a small portion of the flame retardant is effective. It has been found that additives which are able to trap alkali metals, especially calcium, under certain conditions in the formation of stable calcium compounds, prevent interference with the flameproofing effect. The first additive is MgC.
03, MgS04, K2C204, K2C03, AI2
Compounds such as (S04)3 and K2S04 are suitable. The additives are used in amounts of 1 to 1% by weight, preferably 5 to 1% by weight, based on the total weight of polymer, glass fibers, flame retardant and additives. However, even without the above-mentioned additional additives, the flameproofing effect is still significant when using the above-mentioned glass fibers and is already sufficient for many applications. Of course, the combination of the additives mentioned can also be carried out in the case of other alkali metal-containing reinforcing materials as well as in the presence of other alkali metal-containing additives. The object of the invention is any heat-resistant and optionally self-extinguishing polymer composition obtainable on the basis of said method,
These are obtained using the oxalato rust bodies mentioned above and in particular contain 1 to 4% by weight, preferably 5 to 15% by weight, of oxalato rust bodies. The rust salts used in this invention have many advantages compared to known flame retardants. First of all, they are obtained very simply from the starting materials, oxalic acid, inorganic metal salts or metal hydroxides and optionally simple inorganic alkali metal salts; the preparation in this case takes place in aqueous solution. With the exception of calcium and rubidium salts, conventional halogen, phosphorus, nitrogen and/or
Or, it is significantly cheaper than products containing SQ03.
Since the effect of the complex salt according to the invention is better than that of flame retardants of the state of the art, in order to obtain a comparable flame retardant effect, very low weight % additions to the polymer are required. That's enough. Therefore, the properties of the treated material are hardly changed. The compounds of the present invention have extremely good compatibility with the skin. Also, no plexus gas is generated during the combustion process. C02 is formed as the only gaseous combustion product of these materials. Dripping of the polymer melt is furthermore prevented by incorporating the complex salt according to the invention. Example
1-14 Oxalato complex 10
% to 20% by weight. The extrudates were processed into polyamide films with a thickness of 2 willow; the corresponding ΔLOI values are listed in Table 2. This LOI-value was calculated based on ASTM-D2863 by Stanton Redcroft & Co.
n) Measured using a measuring device located in the United Kingdom. The LOI-value (Limiting Oxygen Index) is determined as the oxygen concentration of the oxygen-nitrogen mixture at which the top of the vertically erected sample can continue to burn. The ΔLOI-value corresponds to the difference between the LOI-measured value of the flame-retardant sample and the LOI-value of the non-flame-retardant sample. The following Oxalato body was used: K2 [Mg (C204
)2] D. P. Gratsdon, “J. lnorg & Nu.
cl. Chem. ''1956, Volume 3, Page 321, Produced by method 1: Potassium oxalate monohydrate Matayu (0.206 mol) was dissolved in 5 portions of water, the solution was heated to boiling, and water was added. 100 Magnesium chloride underground 20
．． A solution of 3 mol (0.1 mol) was added. The mixture was heated for about 1 hour. After cooling to room temperature, the precipitate was placed in a suction furnace, washed free of chlorine with water and finally evaporated in vacuo for 15 minutes.
It was dried at 0°C. The yield was 20 min (72% of the theoretical value). K2[Zn(C204)2]/K4[Zn(C
204)3]D. P. Graddon, “J1nor
g. & NucIChem. ''1956 Sheep, Volume 3,
Page 321, prepared according to method 1: A solution of 57.5 moles (0.2 mol) of zinc sulfate heptahydrate in 200 parts of water was added to a solution of 100 parts of potassium oxalate in 100 parts of water. Hydrate 36.
8 ml (0.2 mol) in a hot solution. The zinc oxalate produced was heated in an absorption oven and washed with cold water. The zinc oxalate thus obtained was then introduced into a boiling solution of 75 molar potassium oxalate monohydrate (0.47 mol). The resulting clear solution was dried for about 30 minutes, diluted to about 150 ml with water and cooled. A precipitate was deposited during grinding using a glass rod. This was passed through an absorption furnace, first in vacuum at 10,000 degrees, and finally at 150 degrees.
It was dried at o. The yield was 54 min (55% of theory). This substance is K4 [Zn(C204)3] and K2 [
Zn(C204)2] and 39
It had a decomposition point of 5-43,000. K[Zr(C2
04) 4] 23.3 ml of zirconium chloride (0.1 mol) to 1 mol of methanol
It was dissolved in 50 places. The solution was filtered and introduced at room temperature and under water into a solution consisting of 100 parts methanol and 20 parts oxalic anhydride (0.22 mol). In this case, a precipitate separated out. The batch was left at room temperature for about 2 hours and then heated. The precipitate was thoroughly washed with methanol, then dissolved in 100 g of water, then filtered and finally concentrated with 100 g of water and 40 g of potassium oxalate monohydrate (0.24 mol).
was placed in a hot solution of The precipitate deposited during this time was filtered through a suction oven, washed with methanol and dried at 150° C. in vacuo. The yield was 43 days (72% of the theoretical value). K
Ba [AI (C204) 3] K3 [AI (C204) 3] 40.8 m (0.1 mol)
was dissolved in 200 ml of hot water. This solution was cooled to about 30° C. and a solution of 22.4 molar barium chloride dihydrate (0.1 mol) was added dropwise under the pressure. In this case, a precipitate separated out. The batch was incubated for about an additional hour and allowed to stand for an additional 2 hours. Finally, the precipitate was filtered, washed chlorine-free with water and dried at 150°C. The yield was 46.6 days (46.7% of theory). K3 [AI(C204)3] This complex salt is described in J.
C. Bailar and E. M Jones (
Jones), “Inorganic Syntheses”
1'' (1939), p. 36. The analytical results of the products obtained in various batches are published in K.
I (C204) Shino] and K3.36 [AI (C2Q) 3
．． 46]. R Hiro [AI (C204) 3] Rubidium-aluminum-trioxalato rust was synthesized as follows in 'ChemRev. 61” (
(1961), pp. 213-246]. Water 43 underground N2 (S04) 3.18LO In a hot aqueous solution of 9.65 days (0.0144 mol), water 15
A solution of 3.46 molar (0.0864 mol) of underground sodium hydroxide was charged. The precipitated sodium hydroxide was separated from the furnace, washed, and mixed with 50% water and 10.88% oxalic acid (0%
．． 0864 mol) in a boiling solution. At this time,
A clear solution was obtained. Add 1 part of water to this solution at 10,000
A solution of 10 molar rubidium carbonate (0.0433 mol) was added dropwise and heating was continued for 30 minutes. The solution was then separated from the light emulsion (unreacted aluminum hydroxide formed by neutralization) by filtration and finally cooled. The oxalato rust was then precipitated by adding methanol and subsequently passed through a suction oven and heated at 150oC in vacuo.
It was dried with. The yield was 13 days (82.5% of theory). K2 [Fe(C204)2] Literature: Sacchie (
Suchay) and Rensen, An.
n. 105, 255 Franke, Ann
．． 491, 46 Gmelin, Eisen, B K2C204 20184 mol (1 mol) was heated with 200 mol of water until it became a solution and under nitrogen the FeC 204 2LO IIO 2 mol (0.61 mol) in the water 200 mol.
A suspension of was added. The reaction mixture was dried while additional K2C204 was added until the insoluble portion of FeC204 was dissolved. For this purpose, water is 250 K2C204 dissolved in the ground.
・Sunday 2040 evening was required. The red solution was cooled and further stirred, during which time salt gradually precipitated.
The product was dried in a suction oven almost air-dried for a week and then dried in vacuo at 50 qo for 1 hour. Yield is 170
It was evening (90% of the theoretical value). KBa[Fe(C20
4) 3] Ratio C204/H2037.8 (0.3 mol) to water 20
It was dissolved in 0. Heat the solution to boiling and add iron oxide (m) hydrate [product of Riedel de Haan, iron content 53-54%; total 1 mole of Fe] 10.53
Added evening. After dissolving the iron oxide hydrate, first add 6.9 moles (0.05 mol) of potassium carbonate in 10 mole of water dropwise,
Then 50% of Ba(OH)2 in water (0.1 mol) was added. In this case a brown substance precipitated out. From the green furnace liquid, the desired rust salt is added first on cooling.
Fraction (59) was produced. Boil the water together several times to get a brown furnace residue and put it in the furnace. From the combined, likewise green furnace liquid, a second fraction of Suzushio 23 was added upon cooling.
The evening was generated. This salt was heated in a furnace and heated in a vacuum for 1500 min.
It was dried at 0. The total yield was 28 evenings (56.5% of the theoretical value)
)Met. Table 2 Examples 19-23 To produce flame-resistant plastics, 10% by weight of K3 [M(C204)3] was blended with various polymers in a conventional manner. In most cases, the polymer as well as the flame retardant are ground and sieved, the powders are then mixed together and placed in a vacuum for several hours.
Dry at 50°C and finally divide the mixture into 3 x 6.5 x 15
The test plate on the 0 side was hot rolled. In the case of polycarbonate, it was dispersed in dichloromethane and the solvent was then removed under vigorous scrubbing and by gradually increasing the temperature. The foam material obtained at this time was heated at 150°C in a vacuum.
The specimens were dried for 1 hour, subsequently milled in the same way and then processed in the same way into test panels. AS the LOI-value of these boards
The Δ01 value was measured according to TMD 2863 and compared with the Δ01 value of a board made of material without the addition of a corresponding flame retardant. The polymer materials used and the ΔLOI values obtained are as follows:
Record in the table. 3

Claims (1)

[Scope of Claims] 1. Flame-resistant and optionally self-extinguishing polyamide, polyolefin, polyacrylate or epoxy compositions, characterized in that they homogeneously contain one or more oxalato complexes as flame-retardant additives. . 2 The oxalato complex is [Z(C_2O_4)_n]＾-
A patent claim containing a complex anion of the ^e type, where Z is one or more central atoms, n is the number of ligands, and -e represents the negative charge of the complex anion. A composition according to scope 1. 3 Mg, Ca, Sr, Ba, where the complex anion is the central atom,
Zr, Hf, Ce, V, Cr, Mn, Fe, Co, Ni
, Cu, Zn, Cd, B, Al, Ga, In, Sn, P
The composition according to claim 1 or 2, containing at least one of Sb and Sb. 4 The cation components of the oxalato complex are ions Li, N
A composition according to any one of claims 1 to 3, containing at least one of a, K, Rb, Cs or NH_4 or one of said ions and Ba. 5 The oxalato complex has the general formula: Me_kIMe_lII [Z(C_2O_4)_m], where MeI represents Li, Na, K, Rb, Cs or NH_4, MeII represents one of the above cations or Ba, and Z represents the central Atomic Mg, Ba, Zr, Fe, Co, Cu
, Zn, Al, Sn, Cr and Sb and k■0, 1, 2, 3 or 4, l■0 or 1 and m■2,
3 or 4] according to any one of claims 1 to 4. 6 Containing an oxalato complex in an amount of 1 to 40% by weight,
A composition according to any one of claims 1 to 5.