DE2002729A1 - Phosphonic acid dialkyl esters, their production and their use as antioxidants - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6668 / -E '. -

Germany

Phosphonic acid dialkyl esters, their production and their Use as antioxidants.

The invention relates to dialkyl phosphonic acid esters the formula

00 9833/2056

C (CH) O

J J Ii

(1) HO— <S> CH ₂ —Nil — CO— (CH ₂ -) _n —P == (OR)

wherein R is an alkyl radical having 1 to 18 carbon atoms and η mean 1 or 2.

Preferred phosphonic acid dialkyl esters correspond to the formulas

C (CH)

(2) HO- ^ O CH ₂ -NH-CO- (CH ₂ -) _n -P = (OR ₁ ) ₂

wherein R _{1 is} an alkyl radical having 12 to 18 carbon atoms and η 1 or 2 and furthermore

C (CH,) 3 O

(3) H0 ^ Q> CH ₂ -NH-CO- (CH _{2) n} -P = (0R _{2) 2}

where R _? denote an alkyl radical having 2 to 4 carbon atoms and η 1 or 2.

Among the compounds encompassed by the formulas (2) and (3), those of are particularly interesting Formulas

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C (CH) O

Li "

wherein η is 1 or 2 and

—Μ — CO— (CH ₂ ) _n -

wherein τι 1 or 2 is.

The compound of the formula is particularly suitable

The phosphonic acid dialkyl esters of the formula (1) are, for example, dimethyl, diethyl, dibutyl, Didodecyl or dioctadecyl esters. Depending on whether η 1 or 2 is used to manufacture various base products this dialkyl ester is used.

If η = 1, the procedure is that after the Principle of the Michaelis-Arbusow reaction (a) a compound of the formula

00 9833/20 56

(7) HO- <I> CH ₉ -NH-CO-CH

C.

wherein Y represents a halogen atom with (b) a compound of the formula
(8th)

^ where R is an alkyl radical with 1 to 18 carbon atoms, condensed. This reaction can be carried out without a solvent or in a suitable solvent such as xylene, be performed. The halogen atom Y in the formula (7) may, for example, be an iodine, bromine or especially a chlorine atom represent.

The starting product of the formula (7) necessary for this reaction is made from 2,6-di-tert-butylphenol and N-methylol-chloroacetamide obtained by Tscherniak condensation. This latter implementation is known and is used in French Patent No. 1,571,696.

The compounds of the formulas (2), (3), (4) and (5) with η = 1 are accordingly obtained by using as a component (b) a combination of the formulas

(9) PC-OR ₁ J ₅

(10) P (-0R ₂ ) ₃ ,

(11) P (-OC ₁₈ H ₃₇ ) ₃ and

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ί-12} Pf-OCi H)

\ • ⁱ - ^c - I ^ \ V ^ h Q '"X

wherein R ₁ and R _{p have} the meaning given, is used.

Phosphonic acid dialkyl ester of the formula (I), wherein
η = 2 isti are obtained by adding
(a) a compound of the formula

(13) HO- ^ Ö ^ -CH ₂ -NH-CO-CH == CH ₂ , with

(b) a compound of the formula

o. -. ■ · ■■ -

II
(14) H-P === (0R) ' _o . ,

wherein R represents an alkyl radical having 1 to 18 carbon atoms. This reaction is conveniently carried out in an anhydrous medium, for example a suitable organic one
Solvents such as absolute dioxane, tetrahydrofuran or
l ^ -Dimethoxyethane carried out, the reaction is carried out by
the presence of small amounts of the sodium salt of the corresponding compound of the formula (IA), which is first formed in situ by the addition of metallic sodium, catalyzes,

The output module required for this reaction
of the formula (13>) katin from 2, β-di-tert-tertiary-butyipiienQl
and N-Methyloi-siQrylamld by !! s.cheEniak condensation iri.

Glacial acetic acid can be obtained in the presence of pyrophosphoric acid, as already described in French patent 1,475 has been described.

A more rational way of preparing the compound of formula (13) consists in the same reaction, only that the pyrophosphoric acid is replaced by gaseous hydrogen chloride. A 1: 1 addition product initially falls directly the compound of the formula (13) and N- (3 * 5-di-tertiary-butyl-4-hydroxyphenyl-methyl) -ß-chloropropionamide the end:

G (CH ₃ ).

C (GH ₃ J ₃

H ₂ -NH-C-GH = CH ₂ + HO <O

C (CH,).

(1: 1)

Obtained from the addition product of the formula (I.5) by splitting off HCl using sodium hydrogen carbonate the compound of the formula (13) in good yields

The compounds of the formulas (2), (3), ( ² O and (.5) with η = 2 are accordingly obtained in that ¹ is a compound of one of the formulas as component (b)

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(16) H-P =

■ S

(17) Η-P == (0R ₂ ) ₂

O '
(18 j H-P == (OC ₁₈ H ₃₇ ) ₂ or

0
(19). HP =

used, in which R. and Rp have the meaning given.

The phosphonic acid dialkyl esters of the formulas (1) |

to (6) -are used as antioxidants for plastics. As plastics, polyethylene, polyurethane and especially polypropylene come into consideration; also polyvinyl chloride and rubber. . . .

In protecting oxidation sensitive plastics against oxidation is conveniently moved so that: one of these plastics, a small amount, preferably from 0.01 by weight to 2% on the amount of the protected resin, at least one compound of the formulas (1) \ • to (6 ) incorporated. . ^

. . _: . . , The compounds of the formula (1) can be incorporated into the plastics to be protected, for example. Directly, ie alone or together with other additives such as plasticizers, pigments, light stabilizers, optical brighteners,

00 98 3 3/2 056

means ^ other antioxidants and / or with the help of solvents be incorporated.

The combined use of the compounds of the formulas (l) to (6) together with flame retardants, in particular those which contain phosphorus show certain advantages, especially in polyurethane coating compounds. In addition to the actual antioxidant effect, the compounds are capable of the formulas (1) to (6) namely also to significantly increase the flame-retardant effect of the flame retardant.

The use of the compounds of the formulas (1) to (6) in combination has proven to be particularly advantageous with other antioxidants, namely sulfur-containing carboxamides.

These carboxamides are known from French patent 1,571,696 and correspond to the formula

0
(20) R ₁ -CH ₂ -NH-C- (CH ₂ ) _m - (S) _n -R ₂

wherein R _{1 is} a benzene radical which carries a hydroxyl group in the o- or p-position to the -CH ^ group and two hydrocarbon radicals as further substituents, Rp a hydrogen atom, an optionally further substituted alkyl or aryl radical, a radical of the formula

0
(21) - (CH ₂ ) _m - C-HN-CH ₂ -R ₁

009833/2056

in which R 1 has the meaning given and m is an integer with a value of at most 2 and η is an integer with a value of at most 7. Carboxamides of the formula (20) in which the radical R _p bears several thloether radicals are preferred. In particular thioethers of the formulas

• (22)

HO-CL: C

G — CH ₂ -S-

and

(23)

C (CHj.

have been used in combination with the phosphonic acid alkyl esters of formulas (l) to (β) have proven particularly advantageous.

The quantitative ratio between the phosphonic acid dialkyl esters of formula (I) and the sulfur-containing carboxamides the formula (20) in combination preparations fluctuates within wide limits. For example, Preparations proven the 20 percent by weight, of a compound of formula (20) and 80 percent by weight of a compound of formula ■ (1).

In general, the combination preparations show a better antioxidant effect than the individual components

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ten to yourself.

Percentages in the following preparation rules and examples are percentages by weight.

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Manufacturing regulations

51 * 5 g of 2,6-di-tert-butylphenol and 26.5 g N-methylolacrylamide are successively under gentle Warming »dissolved in 50 ml of glacial acetic acid. Then you lead under Stir and exclude moisture until HCl gas is saturated. The reaction is exothermic; through external cooling keep the temperature at 30 ° C.

A thick precipitate separates out during the reaction. The mixture is then stirred for a further 3 to 4 hours at room temperature and then for a further 1/2 hour at 5 to 10 ° G. It is then filtered off sharply and washed with a little glacial acetic acid. The filter residue is stirred up with 1 liter of water, filtered off with suction and washed with water. 57.7 g (= 75 % of theory) of the 1: 1 addition product of N- (3 * 5-di-tertiary-butyl-4-hydroxyphenyl-methyl) acrylamide and N- (3,5-di) are obtained -tertiary-buty1-4-hydroxypheny1-methy1) -β-chloropropionaemide; Melting point: 168 to 171 ° C. This product can be recrystallized without decomposition and without changing the melting point from acetone or chloroform.

An aqueous suspension of this product initially reacts neutrally, but after a short time becomes acidic.

009833/2056

The 1: 1 addition product is taken together with 16.8 g of sodium hydrogen carbonate and 200 ml of acetone Stir refluxed for 1 hour. One cools down, sucks off the undissolved inorganic material and removes it Solvent in vacuum. The oily residue crystallizes quickly after inoculation. 54 g of N- (3,5-di-tert-butyl-4-hydroxyphenyl-methyl) acrylamide are obtained of melting point 107 to 109 ° C, which corresponds to the formula (13).

It is recrystallized from 400 ml of cyclohexane

fe and obtained 47.1 g (= 65 $ of theory based on 2,6-di-tertiary-butylphenol) acrylamide having a melting point of 112 to ⁰ II3 C.

The acrylamide of the formula (13) can also be derived from the 1: 1 addition products in an almost quantitative manner Gain yield by vigorously stirring the latter with excess 2N sodium carbonate solution for several hours and after the sodium carbonate solution has been suctioned off, it is washed until the reaction is neutral; Melting point: 110 to 111.5 ° ^. ) The substance is produced by this latter method, not completely free of bound chlorine.

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example 1

18 g of N- (3,5-di-tert-butyl-4-hydroxyphenylinethyl) chloroacetamide are in 50 ml of dry xylene

Ί -

solved by heating. 7.2.2 g of trimethyl phosphate are added and the mixture is refluxed to a gentle boil. The reaction is over when the reaction solution no longer contains any bound chlorine, which can easily be followed by occasional sampling and testing using the Beilstein reaction. A gentle refluxing of 0 to 45 hours is sufficient.

Afterwards it is cooled down, after which the product precipitates out after a short time. One receives 16.2 g (= 73 $ of the theory) a compound "from the melting point (after recrystallization from benzene or from xylene) from 142 to 145 ° C, that of the formula

C (CH) 0

HO-C3

is equivalent to.

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Example 2

The procedure is analogous to that in Example 1, using triethyl phosphate (instead of the trimethyl ester) in the stoichiometric amount. Yield: 62% of theory; Melting point (after recrystallization from xylene or cyelohexane): 97 to 99 ° C. The ^ compound corresponds to the formula

C (CH) O

^^ Il

HO — CZ> CH ₀ —NH — CO — CH ₀ —P = (OC ₀ H)

(25) I ^{d ά} ^ Dd

Example 3

18 g of N-iJ ^ -di-tertiary-butyl-'il-hydroxyphenylmethyl) chloroacetamide and 14.6 g of tributyl phosphate are put together in a reflux apparatus with an air cooler Heated to 175 ° C. (bath temperature) for 2 hours. Meanwhile, nitrogen is passed into the reaction vessel around the to drive off any butyl chloride through the reflux condenser.

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It is then cooled and crystallized from 80 ml Cyclohexane around. You get 20 g (= 73 $ of theory) one Compound of Formula (26).

A larger sample is chromatographed on silica gel with an ascending series of benzene-chloroform eluents purified and then recrystallized again from cyclohexane; Melting point: 91 to 92 ° C.

σ (CH ₃ )

Example 4

In a distillation apparatus with a stirrer, 9 g of N- (3,5-di-tertiary-butyl - ^ - hydroxyphenyl-methyl) chloroacetamide and 17 g of phosphorous acid tridodecyl ester are stirred at 175 ° C. for 2 hours at 15 mm Hg pressure finally heated to 200 ° C (bath temperature). Here distill at to 148 ⁰ C "and 15 mm Hg pressure 3.75 g C = a 6y>% of theory) dodecylchloride.

The residue is - after cooling on Kieselger with ascending eluent series benzene-chloroform

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chromatographed, giving 15 g (= 75% of theory) of a waxy-crystalline product with a melting point of 47 to 49 ⁰ C, that of the formula

(27) '. ην -% ==? cü ₂ -j) jh-oü-üü ₀ -p = r ^ UC ₁₂ H ₂₅ ; ₂

^ corresponds to.

Example 5

a) 9 g of N- (3,5-di-tert-butyl-4-hydroxyphenyl-. methyl) -chloroacetamide and 24 g of phosphorous acid trioctadecyl ester are stirred for 1 1/2 hours in a distillation apparatus at 0.001 mm Hg pressure 175 to 185 ⁰ C (bath temperature) heated. Octadecyl chloride distills off, contaminated by some N- (5,5-di-tertiary-butyl-4-hydroxyphenyl-methyl) -chloroacetamide, which partially sublimates off under these conditions. The distillation residue is recrystallized from acetone and then from petroleum ether, the desired product of the formula (28) being a hard wax-like crystal mass

.nkt: 71.5 to 7 009833/2056

accrues; Melting point: 71.5 to 72.5 ° C.

C (CH) O.

^ --— CH ₂ Hp-CQ-CH ₂ -! ^

b) 9 g -N-3-, 5-di-tert-butyl-4-hydroxyphenyl- · - methyl.) - chloraoetaraid. and £ ζ> jal dry xylene are stored at a bath temperature of 175 ° C. heated under reflux for 90 hours under nitrogen. The solvent is then removed in vacuo and the waxy residue is purified as described in Example 5a); Melting point: 71 * 5 to 72.5 ° C. ■ ■ '. . "

Purification can also be done by chromatography on silica gel with ascending series of eluents benzene-chloro -form ethyl acetate.

The compound of the formula (28) is obtained

Example 6

-i 27/6 -g 'PhasphoiPtgsaurediathylester are ih' 150 ml of absolute M-oxane ^ 'dissolvedOsW.' -Man ^ are 0 ', 5 g of sodium to' and, stirring ^·:; 15 ^{; -Hour:} unt'er 'StTc'fcstoff / where the sodium-on. Dissolves ^- and es- · a ^v gerihge Menge'eines created ¹ flo'ckigen precipitate. ■ '■■ "■■ - ^ -"'" ^J '' '■ -'""

00983

57.8 g of N- (3,5-Dl-tertiary-butyl-4-hydroxyphenylmethyl) acrylamide are then added to, which dissolves quickly and stirs, still closed, for 25 hours. then the solvent is removed completely in vacuo. The resinous residue is recrystallized from dry benzene and the crystals are dried in vacuo for a long time. 55.7 g (= 65 $ of theory) of the product are obtained Melting point 104 to 106 ° C, that of the formula

^ uvun ";" 0

_(2g yes »^ - w -CH ₂ -NH-CO-CH ₂ GH ₂ -P = (OC ₂ H ₅

is equivalent to.

Example 7

7.76 g of phosphoric acid dibutyl ester are in

^ 30 ml of absolute dioxane dissolved. 0.1 g of sodium is added and stir under nitrogen for 15 hours; in the process, the sodium dissolves and a small amount of one is produced flaky precipitation. 11.57 g of N- (3,5-di-tertiary-butyl-4-hydroxyphenylmethyl) acrylamide are then added to, which dissolves quickly. The reaction mixture located in a closed vessel is then stirred. 3 days long.

009833/20 E6

and then heated for 2 hours under nitrogen Reflux: to boiling. . '

The solvent is now completely in the vacuum removed and the waxy-crystalline residue -Cyclohexane recrystallized. One receives 12.6 g (= 65 # of theory) of the compound from melting point 113 to 116 ° C, that of the formula

H0 ~~ <Q C (CH

GH ₂ -NIMJO-CH ₂ Ch ₂

is equivalent to,

Example 8

17 * 6 g of dioctadecyl phosphate are dissolved in 100 ml of absolute 1,2-dimethoxyethane with heating. 70 mg of sodium are added and the mixture is refluxed for 18 hours under nitrogen and stirring. The sodium dissolves and a small amount is formed To this are added 8.67 g of N- (J, 5-di-tertiary-butyl- ^ - hydroxyphenylmethyl) acrylamide,

009833 / 20B6

ches dissolves rapidly and heated under nitrogen 24 Hours at reflux.

It is then left closed for 2 days at room temperature, with a large part of the product crystallized out. Another portion is obtained by concentrating the mother liquor.

The cleaning is done by recrystallization from a lot of petroleum ether. 15.5 g (= 58% of theory) of the compound with a melting point of 76 to 78 ^° C. and corresponding to formula (31) are obtained.

The crude product can also be dissolved in chloroform and then purified by chromatography on silica gel. The substance is obtained as a chloroform adduct; Mp 35-36 ⁰ C, it is determined again on further heating, and melts finally at 72-7 ^ ° C. For this adduct can be the chloroform by heating in a high vacuum cleaved (at l6O ° C / 10 minutes / 0.001 mm Hg).

C (CH)

(3D L ³

C (CH ₃ J ₃

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SSI

Example 9

A mixture of 20% thioethers of the formula (22) or (23) and 80 % of the phosphonic acid dialkyl ester of the formula (2?) Is heated to 130 ° for 1 minute with stirring in the middle of the handle . C or. L65 ° G, with cloudy to clear melts; develop,. Then you 'deter' by cooling with · cold 'water \ .;. , -.: ...- -.:v·.- -: ty. . ^:: . ·: ·; '

The following combinations were jiaeh -this ^ Ver. drive won ί ■ ^: - '"· ■" ■■■ - ^: '; ■ '- ■ -; ■ .- ■ -:,.;> - -; , _v -: ■ -

■ --.- '.' ■ T a .b. e 1/1 e, T

mixture Thioether
the formula ._ phosphonic acid
dialkyiester
the formula - '- consistency A.
B. (22)
^(.25); (27)
(27) "■ ^ resinous
: resinous -.

Testing of the anti-oxidative effectiveness

A mixture of 100 parts of unstabilized

00 9 8 33/2056

Polypropylene and 0.2 parts of a dialkyl phosphonate of the formula (l) or their combination products with thio ethers of formula (20) is processed on the calender at I70 C ⁰ zueinem coat. This is then at 230 C and

2
pressed at a pressure of 40 kg / cm to a plate 1 mm thick . The plate is cut into narrow strips and left to age in an oven at 140 ° C. until clear cracks can be seen with the eye.

The results are summarized in Table II. For comparison, those with the thio compounds are also shown in Formula (22) or (23) indicated the aging times that can be achieved alone. From the values it can be seen that the combination the phosphonates with the thio compounds even gives better protection against aging than the individual compounds alone.

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Table II

"Zugo & et-zte connection
the formula
or combination Time to crack
education in hours without addition 5 . (25) 35 (26) 75 (27) 600 (28) 1000 (29) 25th ; (3O) 60 (3D 530 (22) 500 (23) 600 A. 1100 B.
φ - -1000

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Example 10

Mixtures of

100 parts rubber (latex cr§pe)

5 parts of zinc oxide

10 parts of titanium dioxide

75 parts of barium sulfate

1 part stearic acid

1.5 parts of 2-mercaptobenzothiazole

2 parts of sulfur

and 1 part of one of the compounds of the formulas (25) *

(26), (27), (30), (31) or the combination B (see example 9)

are homogeneously mixed on a two roll mill at βθ C during JO minutes, followed by vulcanization for 20 minutes in a press at l4o ° C to 1 mm thick plates pressed. From this, dumbbell-shaped, 8 cm long test specimens are punched out, which are then aged in an oven at 100 ° C. for 50 hours. By measuring the breaking load and the elongation at break, before and after aging, one can see the decrease in mechanical strength or the antioxidant effect of the above-mentioned compounds.

The results are summarized in Table III. The stated values are average values from 5 samples each.

In Table III:

L = breaking load in kp / mm
D = elongation at break in %

009833 / 20B6

_Β ty ρ-- _

Table III

Antioxidant the mechanical : Oven aging 100 ⁰ C O 50 acceptance Formula "or combination strength Booths : '1.29' 1.03 in fo nation • 910 772 ; '1.52V 1.36 without addition 976 814 20th : ^B. 1.32 1.21 20th (25) :> ■ L. ^:: ' 934 800 9.1 ; B. . - '1.51' : 'l, 33 16.4 ; L. 1012 877 ■ 8th (26) ' : B. 148 . .1.39 14.3 (27) L. 932 802 12th ■ '■ ■■ -' ■ · '■■■ ; "■ '" ■ -' D ■ .-: .-. 1.24 1.1 .13.2 ι "'■ · 930 772 '- ■ 6 (30) ■ B. : n.Lr 1> 31 . .. 1.18: · 14th • '■ ·; ■ · -. ■ ·. r ■: ν : ■,: ■■> i: '.' ■ - "- ■ ^:. ■ .- ■■ '-
• L . 944 824 11th (31) B. "''17 r> \ ·; -, i ".'- -, - ■. ■■ '· - ·' · . 10 _: '. JJ B. , 12 »7

Example 11

100 parts of polyethylene granules are mixed with 0.2 parts each of the compounds of the formulas (25), (26), (27), (28), (29), (30), (31) or the combinations A or B dry-blended and then processed on a two roll mill at l4o ° C for 3 minutes to form a homogeneous Pell. This is then pressed in a press at 150 ° C. for 5 minutes to form a film 0.2 mm thick. This necessary for the dumbbell-shaped rice experiments, 8 cm long specimens are punched out, which are then aged in an oven at 85 ⁰ C for 200 hours. By measuring the breaking load and elongation at break, one can see the decrease in mechanical strength or the antioxidant effect of the above-mentioned compounds.

The results are summarized in Table IV.

ψ The stated values are average values from 5 samples each.
It means:

L = breaking load in kp / mm
D = elongation at break in %

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Table IV

Antioxidant the
Formula or combination
nation mechanically
strength Oven aging 85 ° G
-
Hours ' 200 acceptance
in $> without addition L.
D. 0 1.06
248 23
33 (25) I.
D. 1.38
370 1.32-
380 8.2
4.2 (26) L.
D. 1.44
397 1.30
379 9
3.2 (27) L.
D. 1.43
392 1.34
399 14th
9.3 (28) B. 1.56
440 1.18
327 15th
14.2 (29) : ■ ι ...
D. 1.39
381 1 * 21
378 19.3
12.6 (30) L.
D. 1.5
435 1.21
346 16.5
19th 1.45
428

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Table IV (porting)

Antioxidant the
Formula or combination
nation mechanical
strength Oven aging 85 ° C
hours 200 acceptance
in $> (3D I.
D. O 1.16
330 20.4
19th A. L.
D. 1.46
407 1.29
333 16
26th B. L.
D. 1.54
451 1.36
407 3.5 1.41
407

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..., '■ .., .-. "2002723

Example 12

"1ΘΌ parts polyethylene powder with 0.2 'parts of the compounds of formulas (.25) (.26), (27), ■ ■ - · ^(28); (2 ^ ^KO. Q} . * dW or combinations Ä or B ^ .gemischt dry and ansehliessend; on:; processed into a homogeneous coat This' is then "too in a press at 13O C for 3 minutes, two-roll mill at 110 C for ¹ J.- minutes. .A 1 ram thick plate is pressed y ^

which are aged in an oven at -85 C for 72 hours. To determine: the melt index, the plates aged in this way are: comminuted into small chips. The melt index is determined in accordance with ASTM D-I238-62 T, method E (weight 2.16 kg, temperature 190 ⁰ C, time 10 minutes). The increase in the melt index or the antioxidant effect of the above-mentioned compounds can thus be seen.

Table V

Antioxidant the Melt index in grams 72 Formula or combination
nation Oven aging 85 ° C
hours 5.121 0 4,827 - 3.525 4,560 (25) 3.828 ■ 4,992 (26) 3.934 4.903 (28) 3.749 4.927 (29) 3,937 4.831 (30) 3,930 4.802 Ä 3.741 B. 3.749

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example

In "a" polyurethane coating compound

20 g isocyanate-modified polyester,

Ig reaction accelerator,

1 g of polyfunctional isocyanate as a crosslinker and

5 ml of ethyl acetate

5 % of the compound of the formula (25) or (29) or · of the mixture consisting of 1 part of one of these compounds

and 9 parts of a commercially available flame retardant ή

■ - ■■■ '■ , "*

of the formula bis (2-hydroxyethyl) amino methane phosphonic acid ethyl ester, stirred in. These mixtures are knife-coated onto flame-resistant cotton fabric in a thin layer (0.5 mm) and cured in air at room temperature. The so
Manufactured test items are subjected to the flame test according to DIN
53906, the oven aging at 85 ⁰ G and the exposure in
Subjected to Xenotest.

From the results in Table VI it can be seen that an admixture of the compounds of the formulas (25) or | (29) the flame retardant effect of the flame retardant
increases significantly.

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Tabel

VI

Addition to poly Flame test Furnace aging • track
yellow Exposure in urethane coating according to DIN 53 906 85 ° C / 85 hours Xenotest select mass track
yellow rend 20 hours without addition burns very much track colorless intensive yellow 5 # bis- (2-hy- hydroxyethyl-amino-
methane phosphonic burns down very yellowish acid diethyl ester yellow (= FSM) 4.5% FSM + 0.5 fi the ver
binding of For self
going out colorless mel (25) $ 4.5 FSM +
0.5 # of the ver
binding of For self
going out colorless mel (29)

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Claims (1)

20D2729 Claims ■ Dialkyl phosphonate of the formula HO - «_ 3 wherein R is an alkyl radical having 1 to 18 carbon atoms and η are 1 or 2. Phosphonic acid dialkyl ester of the formula -CH ₂ -NH-CO- (CH ₂ ) _n -B = (OR ₁ ) ^s where''R-, an alky'irest with 12 to 18 carbon atoms and η 1 or 2 mean. ^:: 3 · Phosphonic acid dialkyl ester of the formula C (CH) 0 JUv Il HO — Ö * CH ₂ -NH-CQ- (CH ₂ ) _n ~ P = (OR ₂ ) where R _{p is} an alkyl radical having 2 to 4 carbon atoms and η 1 or 2. 4. Phosphonic acid dialkyl ester of the formula C (CH) 0 o-C> -CH ₂ -Im-co- (CH ₂ ) _n -p = (oc ₁₈ H ₃₇ ) ₂ wherein η is 1 or 2 5 · Phosphonic acid dialkyl ester of the formula G (GE ₃ ) ₃ HO-CI> -CH ₉ -NH-CO- (CH ₂ ) _n -P = (OC ₄ H ₉ ). wherein η is 1 or 2. 6. The compound of formula C (CH) 0 ■ HO- <t> _{--CH 2} -NH-CO-CH ₂ -P = (0- G (GE ₃ ) ₃ 00 9833/205 6 7. Method for Her alternating ring of phosphonic acid dialkyl esters the 'formula. O ^ ~ CH ₂ —NH — CO-CH ₂ -P = (OR) where R. is an alkyl radical with 1 to 18 carbon atoms ι ■ - interprets, characterized in that one * j (a) a compound of the formula HO-C3> CH ₂ -NH-CO-CH ₂ -Y C (CH _x ) wherein Y represents a halogen atom with (b) a compound of the formula P (-OR) ₅ where R has the meaning given, condensed. 8. The method according to claim 7, characterized in that a compound of the formula PC-OR ₁ ) ,, in which R ^ is an alkyl radical having 1 2 to 18 carbon atoms, is used as component b.). 009833/2056 9 · The method according to claim J _s, characterized in that as component (b) a compound of the formula where R _? represents an alkyl group having 2 to 4 carbon atoms is used. 10. The method according to claim 7, characterized in that the compound of the formula is used as component (b) used. 11. The method according to claim 9 *, characterized in that that as component (b) a compound of the formula PC-OC ₄ H ₉ J ₃
used. 12. Process for the preparation of phosphonic acid dialkyl esters of the formula HO— <r_> —CH "- 009833/2056 wherein R is an alkyl radical having 1 to 18 carbon atoms means, characterized in that (a) the compound of the formula HO- 3 —CH ₀ —NH-CO — CH = CH. ι ² ν--. ■■ - ■ '■ .- ■. ^: ■ -. ί (b) a compound of the formula 0
HP = (OR) wherein R has the meaning given, converts. 13. The method according to claim 12, characterized in that that as component (b) a compound of the formula η— F wherein R 1 is an alkyl radical; with 12 to 18 carbon atoms means used. · _. · l4. Process according to Claim 12, characterized in that component (p) is a compound of the formula H - P = 009 833/20 56 wherein Rp is an alkyl radical having 2 to 4 carbon atoms means used. 15. The method according to claim 13, characterized in that there is a compound of the formula as component (b) used. l6. Process according to Claim 14, characterized in that component (b) is the compound of the formula It used. 17 · Use of phosphonic acid dialkyl esters of the composition specified in one of claims 1 to 6 as Antioxidants for plastics, especially polypropylene. l8. Method of protecting those sensitive to oxidation Plastics, characterized in that mar; these plastics a small amount of at least one phosphonic acid dialkyl ester the composition specified in one of Claims 1 to 6 is incorporated. 19 · The method according to claim l8, characterized in that that the phosphonic acid dialkyl ester in combination with 009833/2056 Carboxamides of the formula wherein R _{1 is} a benzene radical which has a hydroxyl group in o- or p-position to the -CHg group and two hydrocarbon radicals as further substituents, R _{2 is} a hydrogen atom, an optionally further substituted alkyl or aryl radical, a radical of the formula ■ 0 * where R _{1 has} the meaning given and m is an integer i «value of at most 2 and η is an integer with a value of at most 7, is used. 20. By a content of at least one phosphonic acid dialkyl ester the composition specified in one of claims 1 to 6 and optionally at least a carboxamide of the composition specified in claim 19 plastics protected against oxidation, especially polypropylene. 21. Methods of flame retarding and protecting oxidative sensitive substances Plastics, characterized in that one of these plastics has a small amount of at least one Phosphonic acid diacyl ester in any one of claims 1 to 009833/2056 specified composition together with a flame retardant, preferably a phosphorus-containing, incorporated. 009833/2056