DE2712175A1 - Halogen-contg. phosphonate ester flame-proofing agents - for textiles and plastics, are prepd. by reacting epoxide with phosphorus tri:halide, isomerising and halogenating - Google Patents

Abstract

Phosphonate esters are of formula (I): (where A is H, opt. substd. alkyl or alkenyl; R is H, opt. substd. alkyl, aryl or halogen; X is halogen; m = 0 or 1 and n = 0, 1 or 2. A, R and X are opt. identical and >=1 A gp. is X-CH2-CRX-). Suitable textiles are e.g. polyester and/or cotton, and plastics are e.g. polyurethanes, esp. foams. Flame-proofed textiles contain 2-30 wt. % (I). (I) have lower toxicity than standard phosphate-based flame-proofing agents, and low vapour pressure; on burning, hydrogen halide is dissociated over a wide temp. range. Treated textiles have a soft hand. In an example, 1-chloromethyl-2,3-diboromopropane-1-phosphonic acid-di-(2-chloro-3,4-dibromo-1-butyl)-ester was prepd. by (i) reacting vinyl oxirane with PCl3; (ii) isomerising phosphite mixt. and (iii) adding Br2.

Description

Halogen-containing phosphonates

The invention relates to phosphonates of the general formula in which A is hydrogen, optionally substituted alkyl or alkenyl, R is hydrogen, optionally substituted alkyl, aryl or halogen, X is halogen, m is 0 or 1 and n is 0, 1 or 2, and in which the substituents A, R and X are identical or different can, and in which at least 1 radical A is of the formula Process for their preparation, their use as flame retardants and flame retardants which contain Phosp 4ge of the formula (I).

In formula (I), the alkyl radicals contain in particular 1-6, preferably 1-4 carbon atoms, and the alkenyl radicals 2-4 carbon atoms. Preferred substituents are halogen atoms.

For example, 1-o halogen atoms can be present in the alkyl radical. Halogen is understood to mean, in particular, chlorine or bromine.

Aryl stands in particular for phenyl, which is represented by 1 to 3 further radicals can be substituted. Examples of substituents are halogen or C1-C4-alkyl.

Of the compounds of the formula (I) are those of the formula where n has the meaning given and A1 for hydrogen, C1-C4-alkyl or C2-C4-alkenyl, R1 for hydrogen, C1-C4-alkyl, phenyl optionally substituted by chlorine, bromine or C1-C4-alkyl and X1 for chlorine or bromine, and in which the substituents A1, R1 and X1 can be identical or different and at least one radical A1 represents the formula preferably In formula (II), R1 preferably represents hydrogen.

The phosphonates of the formula (I) are prepared by reacting epoxides of the formula (III), optionally mixed with epoxides of the formula (IV), where R has the meaning mentioned, Y is optionally substituted alkenyl and Z is hydrogen, optionally substituted alkyl or aryl, with phosphorus trihalide, especially trichloride, in a molar ratio of 3: 1 to 5: 1 at temperatures between -200C and + 180 ° C, preferably between 20 ° C and 800C. The phosphites that form then become unsaturated phosphonates of the formula at 80 ° C. to 2000 ° C., preferably at 110 ° C. to 180 ° C. in which R, X, m and n have the abovementioned meanings and B stands for Y or Z, where at least one of the radicals B stands for Y, isomerized, and halogen is added to this.

The reaction of the epoxides with the phosphorus trihalide can take place without a solvent or in the presence of solvents which are inert towards epoxides and phosphorus trihalide such as paraffins, chlorinated paraffins, benzene, chlorobenzene or toluene can be carried out.

After the exothermic reaction has subsided, the reaction mixture is still Heated to 60-900C for a certain time, so that there are still residual phosphorus halide residues implemented. Excess epoxide is then distilled off.

This rearrangement reaction of the phosphites can also take place in the presence of 0.1 to 7 mol%, preferably 0.5 to 5 mol%, based on phosphite, of a finely divided Nickel catalyst, such as nickel halides or carboxylates, nickel tetracarbonyl, 7-Allyl nickel halides or carboxylates, Raney nickel or nickel acetylacetonate be carried out, which leads to a lowering of the reaction temperature. at If the isomerization temperature is too high, the formation of dialkylshosshites is increasing or their decomposition products in importance.

According to a preferred embodiment of the method according to the invention for the preparation of the compounds (I) there is a 1 to 10 show excess submitted epoxy compound (III) and optionally (IV) phosphorus trihalide with added dropwise at such a rate that the reaction mixture boils gently. Afterward if the mixture is left to stir for 30-60 minutes, the reflux condenser is exchanged for a distillation bridge and heats the reaction mixture slowly to 75-900C, with excess (III) and optionally (IV) distilled off.

The temperature is now gradually increased to 120 - 1800C.

The rearrangement reaction has ended after 1 to 6 hours. After cooling down at 80 - 1000C any volatile constituents contained in the reaction mixture become removed in vacuo.

The colorless to slightly yellow colored unsaturated phosphonates (V) are under the conditions known for halogen additions (see for example Organikum, 3rd edition 1964, VEB Deutscher Verlag der Wissenschaften, p. 227) with Chlorine or preferably bromine reacted. The halogen addition takes place in stages. Unsaturated halogen adducts can therefore also be included; the location of the remaining Double bonds cannot be characterized in more detail. The remaining double bonds are accessible to the known olefin reactions.

The phosphonates (I) can also be prepared by a different process by reacting halogenated epoxyalkanes of the formula where R and X have the meaning mentioned earlier, with phosphorus trihalides to give the corresponding phosphites and subsequent thermal rearrangement.

However, the intermediate halogenated phosphites at higher temperatures much more sensitive than the unsaturated phosphites, ao that the rearrangement reaction does not always proceed optimally in the desired sense.

Examples of unsaturated epoxy compounds (III) include: in particular vinyl oxirane and 2- (1-chlorovinyl) oxirane, 2-chloro-2-vinyl oxirane, 2-methyl-2-vinyl-oxirane, 2- (1-methylvinyl) -oxirane. As halogenated epoxyalkanes (vI) 2- (1,2-dichloroethyl) oxirane and 2- (1,2-dibromoethyl) oxtrane were possible.

As epoxy compounds of type (IV), for example, ethylene oxide, Propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, glycide and styrene oxide be mentioned.

Phosphorus trichloride and phosphorus tribromide are phosphorus halides called.

The halogenated phosphonates (I) are colorless to dark brown, liquid to solid substances.

The compounds of the formulas (I) and (V) exist as mixtures of isomers. According to NMR spectroscopic investigations, the isomer mixture (V) consists mainly of the isomers (Va) - (Vc), with (Va) predominating.

Examples of the phosphonates of the formula (I) are: A large number of substances with different structures have already been proposed as flame retardants.

The compounds suitable as flame retardants are in particular The following requirements are made: a) They must not be toxic.

b) They should be easy and inexpensive to access.

c) They must adhere firmly to the surface of the substrate.

d) The decomposition range of the flame retardant should be based on the polymer system be coordinated. An elimination of hydrogen halide should be as possible Extend large temperature range so that the flame retardant does not so quickly exhausted.

e) When consisting of halogen and one or more other components Systems, a synergistic effect is desired.

It has now been found that the phosphonic acid esters of the formula (I) meet these requirements to a high degree. They lend out textile materials Synthetic and / or natural fibers, e.g. polyamide, cellulose, cellulose triacetate and especially polyester - and cotton fibers an excellent, permanent flame protection against washing.

They have a low vapor pressure. Their toxicity is considerable among those of known phosphate-based flame retardants. They split when burning the hydrogen halide in a wide temperature range, so that the flame retardant effect is not exhausted so quickly.

The textile materials treated with the phosphonic acid esters (I) have a soft, pleasant feel.

The phosphonic acid esters (I) can be obtained from organic solution or from aqueous emulsion are applied to the textile material.

Preparations are suitable for the production of the treatment liquors which contain 50 - 95% of a phosphonic acid ester (I), an organic solvent and / or water and optionally contain a surface-active compound.

The flame retardants can be applied by dipping the textile material in the organic solution or in an aqueous emulsion of the flame retardants.

The textile material is then squeezed off.

The solutions of the phosphonic acid esters in organic solvents or the aqueous emulsions can also be applied to the Tex.

be sprayed on properly. The application of the flame retardants can be done on dyed or undyed textile material.

If the flame retardant is applied to non-dyed textile goods, is subsequent to the flame retardant treatment, over-coloring or printing of the Textile goods possible.

Following the application of the flame retardants, the textile material dried, for example with hot air of 90-1200 C, and heated, for example for 4 - 5 minutes to approx. 1600 C. Post-heating can also last for 1/2 - 1 Minute at 1900 - 2000 C.

The flame retardants according to the invention can also be used in combination can be applied to the textile material with commercially available disperse dyes.

The flame retardants emulsified in water are added to the dye bath added. Then with the addition of customary dye accelerators at boiling temperature 90 - 120 minutes, or it is treated without dye accelerator according to the high-temperature process, worked for example at 1200 C.

The flame retardants emulsified in water can be used together with disperse dyes can also be applied to a foulard. Then with hot air at 1300 C dried and heated for fixation for 1/2 - 1 minute at 190-2100 ° C.

Suitable solvents for the phosphonic acid esters (I) are alcohols, Ketones, hydrocarbons, chlorinated hydrocarbons and especially mixtures from perchlorethylene with isopropanol.

Commercially available, surface-active compounds, in particular mixtures of anion-active compounds find use with non-ionic substances. Also cation-active compounds can be applied.

Suitable anion-active compounds are, for example, alkylarylsulfonates, e.g. sodium dodecylbenzenesulphonate, alkane or alkene sulphonates, alkyl sulphates, e.g. Sodium lauryl sulfate, alkyl glycol ether sulfates, alkyl polyglycol ether sulfates, alkane phosphonates, Alkyl phosphates, alkyl glycol ether phosphates, alkyl polyglycol ether phosphates or soaps.

Suitable cation-active compounds are, for example, fatty amine salts, quaternary ammonium compounds, amine oxides, derivatives of heterocyclic, higher Bases containing alkyl radicals, such as imidazolinium compounds, amidines, guanidines, Thiuronium salts or sulfonium compounds.

As nonionic surface-active compounds, for example are used: addition products of lower alkylene oxides, especially ethylene oxide and / or propylene oxide to higher alcohols, alkylphenols, fatty acids, fatty acid amides, Alkylamines or alkyl mercaptans, or derivatives of these addition products. Further can fatty acid alkanolamides, fatty acid esters of polyhydroxyl compounds, as well Block polymers of ethylene oxide and propylene oxide and / or butylene oxide are used will.

The flame retardants are used in quantities depending on the type of textile from 4 to 20% of the phosphonates (I), based on the weight of the textile material, preferably applied in quantities of 4 - 8 ,,.

The compounds according to the invention are also excellent Flame retardants for polyurethanes, especially polyurethane foams. They can react to the polyurethane in the production of the polyurethanes Reaction mixtures are added.

The following examples serve to illustrate the invention, the indicated parts mean parts by weight.

Example 1 To a solution of 231 parts of vinyloxirane in 300 parts 137.5 parts of phosphorus trichloride are added dropwise at 0 ° C. to chloroform. After subsiding the exothermic reaction, the mixture is 2 hours. At room temperature and 3 more Stirred at 50 ° C. for hours.

Chloroform and unreacted vinyloxirane are at a bath temperature distilled off from 50 ° C in vacuo. 330 parts (95% of theory) of a clear, colorless one Liquid are preserved.

n20 = 1.4938 D Analysis of the crude product C H Cl P Calculated 41.44 5, lot 30.65 8.92 Found 42.25 5.50 29.50 9.30 According to the NMR spectrum the product is present as a mixture of isomers of 90% as phosphorous acid tri- (2-chloro-3-butenyl-1 ester and 10% as phosphorous acid tri- (1-chloro-methyl-2-propenyl-1) ester. Further By-products are present in amounts below 2%.

50 parts of the phosphite mixture are slowly preheated to 1600C The flask was added dropwise and the mixture was stirred at the same temperature for 5 hours.

49 parts (98%) of a clear, yellow liquid were obtained.

nD20 = 1.5012 According to the NMR spectrum, the starting product is complete rearranged into the phosphonate, with predominantly 1-chloromethyl-2-propene-1-phosphonic acid-dl- (2-chloro-3-butenyl-1 ) -ester is present.

To a solution of 347.5 parts of 1-chloromethyl-2-propene-1-phosphonic acid-di- (2-chloro-3-butenyl-1 ) esters in 1000 parts of chloroform are dissolved 480 parts of bromine in 1000 at 0-5 ° C Parts of chloroform were added dropwise.

After stirring, the solvent is distilled off in vacuo. 817 g of a highly viscous mass remain.

Analysis as 1-chloromethyl-2,3-dibromopropane-1-phosphonic acid-di- (2-chloro-3,4-dibromo-1 -butyl) ester C H Halogen P Calculated 17.40 2.18 70.87 3.75 Found 18.25 2.65 70.95 4.55 Example 2 To 240.0 parts of vinyloxirane becomes 137.5 Parts of phosphorus trichloride are added dropwise at such a rate that the reaction mixture low boiling. The mixture is then stirred for 60 minutes and the bath temperature is increased 75 -900C increased, with excess vinyloxirane over a distillation bridge is distilled off.

The temperature is slowly increased to 1500 ° C. and stirring is continued for 4 hours.

The product has a refractive index of nD20 = 1.5030 and is with identical to the unsaturated phosphonate described in Example 1. By addition the same flame retardant as in Example 1 is obtained from bromine.

Example 3 347.5 parts of the phosphite obtained in Example 2 will be in 1000 parts of boiling chlorobenzene was added dropwise, the temperature gradually increasing rises to over 1400C. After 5 hours the mixture is cooled to 0 ° C. and 480 parts of bromine are added on, stirred and concentrated in vacuo.

810 g of 1-chloromethyl-2,3-dibromopropane-1-phosphonic acid di- (2-chloro-3,4-dibromobutyl) ester will get.

Example 4 A solution of 347.5 parts of 1-chloromethyl-2-propene-1 phosphonic acid di (2-chloro-3-butenyl-1) ester (intermediate according to Example 2) in 1000 parts of chloroform are reacted with 214 parts of chlorine at 0-5 ° C. After two hours After stirring, chloroform is distilled off in a water jet vacuum. The one left behind yellow, viscous mass has the following composition: C12 H18 C13 03 P C H Cl P Calculated 29.41 3.68 50.13 6.33 Found 30.60 4.20 48.80 5.55 Yield: 480 parts of Example 5 271 parts of phosphorus tribromide are added to 232 parts of vinyloxirane added dropwise. After the exothermic reaction has subsided, the mixture is kept at 70 ° C. for one hour stirred and treated in vacuo.

The phosphite formed is added dropwise to a flask heated to 120 ° C and stirred for three hours at the same temperature. The yellow liquid obtained was identified spectroscopically as the corresponding phosphonate.

and20 = 1.5355 481 parts of the unsaturated phosphonate are in 1000 Parts of chloroform at 0-5 ° C. with 480 parts of bromine dissolved in 1000 parts of chloroform implemented. Stirring and subsequent concentration in vacuo gives 940 Parts of a waxy, amorphous mass that partially crystallizes out when standing for a long time.

Example 6 To 138 parts of phosphorus trichloride in 200 parts of chloroform 92.5 parts of epichlorohydrin and then 150 parts of vinyloxirane are added dropwise. It will take an hour Stirred room temperature and the solvent distilled off.

365 parts of a mixture of ClCH2-CHCl-CH2-0-P (-O-CH2-CHCl-CH = CH2) 2 and (Cl-CH2) 2 CH-O-P (O-CH-CH = CH2) 2 are obtained. n20 = 1.5021 CH2-Cl D 2 C H Cl P Calculated 35.68 4.59 38.38 8.38 Found 36.45 5.45 37.60 9.80 100 parts of this Phosphites are added dropwise to a flask preheated to 160 ° C and 4 hours at stirred at the same temperature.

98 parts of a mixture will get.

20 n ° = 1.5030 370 parts of the unsaturated phosphonate dissolved in 1000 parts of chloroform are reacted with 320 parts of bromine in 1000 parts of chloroform and stirred. After evaporation of the solvent, 675 parts of the mixed one are obtained halogenated phosphonates.

Example 7 Polyester fabric made of polyethylene terephthalate with a basis weight of 200 g / m² with a solution of the phosphonic acid ester obtained according to Example 1 in a solvent mixture consisting of 80% by volume perchlorethylene and 20% by volume isopronanol Treated at room temperature, squeezed off, dried for 3 minutes at 110 ° C. and then to fix the flame retardant for 4 minutes at 1600C. The one with 5.8 respectively.

10 wt .-% flame retardant (based on the warm weight) finished fabrics were tested according to the vertical test DIN 53 906-2 / 74 and the following results were achieved: Abbreviations: K r warp; S r shot Sample burning time glow time burning length (s) (s) (cm) KSKSKS untreated tissue 15 19 0 0 17.0 9.5 16 19 0 0 11.0 13.5 19 19 0 0 16.5 17.5 Tissue with 5% 3 0 0 0 6.0 6.0 Edition 0 1 0 0 7.5 6.5 1 0 0 0 7.0 6.0 Tissue with 8% 0 0 0 0 7.5 6.5 Edition 0 0 0 0 7.0 7.0 0 0 0 0 8.0 7.0 Tissue with 10% 0 0 0 0 7.5 12.0 Edition 0 0 0 0 8.0 7.5 0 0 0 0 7.0 7.5 After 25 machine washes at 60 ° C, the following values were measured: Sample burn time glow time burn length (s) (s) (cm) KSKSKS Fabric with 5% 21 | 3 0 0 12.0 | 8.5 Edition 3 3 0 0 7.5 5o 2 2 0 0 7.5 8.5 Tissue with 8% 1 0 0 0 7.5 7.0 Edition 3 0 0 0 7.0 8.0 0 | 0 | 0 | 0 | 7.0 | 7.5 Tissue with 10% 2 0 0 0 7.5 7.0 Edition 1 2 0 0 7.0 7.5 2 1 0 0 7.0 7.0 Example 8 Cotton fabric with a weight per unit area of approx. 200 g / m² is finished with 10% by weight of the flame retardant according to the invention according to the method described in Example 7 and tested according to the vertical test DIN 53 906-2 / 74.

Results: Abbreviations K = warp: S = weft Sample burn time burn length (s) (cm) KSKS untreated 14 15 14 15 blown 13 13 Tissue with 10% 1 0 8.0 7.0 Edition 1 0 7.0 6.5 0 1 7.5 7.0 EXAMPLE 9 Mixed fabric composed of 65% polyester and 35% cotton is finished with 15% of the flame retardant according to the invention according to Example 7 and tested according to the DIN 53 906-2 / 74 vertical test. robe burning time glow time burning length (s) (s) (cm) KSKSKS untreated 11 11 3 3 10 11 3 4 blows 11 12 3 2 15% circulation 6 6 2 2 8.5 | 10 5 6 2 1 9 i5 10 5 5 23 2 9 8.5 Example 10 Component A: 25 parts by weight. of a polyether, produced by the addition of propylene oxide to ethylenediamine (OH number 630), 25 parts by weight. of a polyether, produced by the addition of propylene oxide to ammonia (OH number 550), 30 parts by weight. of a polyester made from adipic acid / phthalic acid (weight ratio 1: 4.2) and glycerol (OH number 240), 20 parts by weight. Glycerine, 2 parts by weight. of a commercially available silicone foam stabilizer, 0.1 part by weight. permethylated diethylenetriamine, 20 parts by weight. 1-chloromethyl-2,3-dibromopropane-1-phosphonic acid di (2-chloro-3,4-dibromo-n-butyl) ester, 10 parts by weight. Monofluorotrichloromethane.

Component B: 187 parts by weight. one by phosgenation of an aniline-formaldehyde condensate obtained polyisocyanate mixture with a viscosity of 100 mPa. s at 25 ° C and des NCO content of 31.5% by weight.

From the reaction mixture of components A and B were in one Aluminum tool heated to 60 ° C, 10 mm thick test plates with a bulk density of 0.6 g / cm3 foamed, from which test specimens for the fire test according to UL-Subject 94 for the mechanical test in the bending test and cut out for the thermal test became.

The determined property values of the material: Flammability classification according to UL-Subject 94 V-O total afterburn time 32 sec.

E-modulus (DIN 53423) 1200 MPa behavior in the heat under bending stress (DIN 53432) 1080 C

Claims (9)

Claims \ j) hosphonic acid ester of the general formula in which A is hydrogen, optionally substituted alkyl or alkenyl, R is hydrogen, optionally substituted alkyl, aryl or halogen, X is halogen, m is 0 or 1 and n is 0, 1- or 2, and in which the substituents A, R and X are the same or can be different, and in which at least 1 radical A for the formula stands0 2) phosphonic acid esters of the general formula where n has the meaning given and A1 is hydrogen, C1-C4-alkyl or C2-C4-alkene. R1 represents hydrogen, C1-C4-alkyl, phenyl optionally substituted by chlorine, bromine or C1-C4-alkyl and X1 represents chlorine or bromine, and in which the substituents A12 R1 and X1 can be identical or different and at least one radical A1 represents the formula stands. .) Process for the preparation of phosphonic acid esters of claim 1, characterized in that epoxides of the general formula optionally in a mixture with epoxides of the general formula where R is hydrogen, optionally substituted alkyl, aryl or halogen, Y is optionally substituted alkenyl and Z is hydrogen or optionally substituted alkyl or aryl, reacts with phosphorus trihalides PX3 to form phosphites, these to phosphonic acid esters of the general formula wherein R, X, m and n have the meaning given in claim 1, and B stands for Y or Z, where at least one of the radicals B stands for Y, isomerizes, and halogen is added to this. 4) Method according to claim 3, characterized in that the Reaction of the epoxides with the phosphorus trihalides in a molar ratio of 3: 1 to 5 : 1 in the temperature range between -200C and 1800C and the isomerization in the temperature range between 800C and 2000C. 5) Process for the flame-retardant finishing of textile materials and Plastics, characterized in that the substrates with Phosponsäureestern des Claim 1 will be dealt with. 6) Method according to claim 5, characterized in that polyester fibers, Cotton or their blends are treated. 7) Method according to claim 5, characterized in that phosphonic acid esters of claim 1 can be used as a flame retardant in polyurethane plastics. 8) Flameproof textile materials, characterized in that that they contain 2 to 30% by weight of a phosphonic acid ester of claim 1. 9) preparations, characterized in that they are a phosphonic acid ester of claim 1 included.