DE2247265A1 - MANGAN (II) SALT OF HALF-STAR PHOSPHONIC ACID - Google Patents

Description

gnLs, the organic material that Vöft Licht slits against the influence of dent siChad. It is known to use manganese salts as light stabilizers flk ⁴ polyamides *, in particular for polyamides matted with fitane dioxide. These are salts of the zxireiwertigen manganese cation with anions of organic acids such as acetate, oxalate, lactate, benzoate. They are the carrier material together with acids of phosphorus, bezw in the form of the corresponding sodium salts or as free acids. their esters, such as sodium hexamethaphosphate, phosphorous acid, phenylphosphonic acid or

30981A / 1234

their esters BEZW before, during or after the polymerization. Polycondensation required. These licfit-stabilizing Ge -...--. Generally, however, they have the disadvantage that they can be partially washed out by aqueous media, which is particularly noticeable after the dyeing of thin polymer structures, for example fibers in aqueous liquors, in a decrease in the amount of chemical waste. The same disadvantage is also shown by pltaepierfire, the only stable polyamide fibers used with the fatty acid salts of organic acids such as manganese.

It has now been found, surprisingly, that new compounds of formula I,

OR

in which R, alkyl with 1 to 18 carbon atoms »cyclohexyl, unsubstituted or substituted by 1 or 2 methyl groups aryl with 6 to 10 carbon atoms or aralkyl 7 to 11 carbon atoms, A is the anion of an aliphatic carboxylic acid with 1 to 18 carbon atoms or an aromatic one Carboxylic acid with 7 to 11 carbon atoms or that Chlorine, bromine or iodine anion, χ 1 or 2, y 0 or 1, where χ + y is 2, and R ″ is alkyl with 1 to 18 carbon atoms mean. ■

are very good light stabilizers for polyamides.

309814/1234

BATH ORIGINAL

The compounds of the invention show over the prior art manganese salts or mixtures thereof with phosphorus compounds as light stabilizers, a significantly improved effect, and also have the desired technical advantage of a significantly lower ability to be washed from the polyamide by aqueous media. Compared to other before-'known light stabilizers for polyamides from the series of salts BEZW. Complexes of hydroxybenzylphosphonic acid half-esters with various other metal ions show a far better light protection effect and much more favorable color properties.

. R- and R «in formula I mean, for example Methyl, ethyl, n-propyl, iso-propyl, butyl, pentyl, hexyl, Octyl, iso-octyl, decyl, dodecyl, tetradecyl or octadecyl.

Preferred for R ^ is alkyl with 1 to 12, and especially

preferably alkyl with 2 to 12 and with 3 to 12 carbon atoms.

Preferred for R are alkyl having 2-18 carbon atoms, such as methyl, ethyl, propyl, butyl or octyl. Particularly preferably methyl, ethyl or butyl.

Aryl under formula I means, for example, phenyl or naphthyl and aralkyl can mean benzyl, 2-

Phenylethyl or Naphthylrr.ethyl possess.

■ '■■ · ■ - ö "

The anion A in formula 1 can be that of an aliphatic Be carboxylic acid with 1 to 1'8 carbon atoms, for example the anion of formic acid, acetic acid, propionic

3098U / 1234 BADORlGmL

f liter, but tiers lure, 2-ethylhexane acid, lauric acid, stearic acid ,

But at dent anion A may also order the · 'one who aroma'tischen a carboxylic acid of from 7 to 11 carbon atoms act to Beispiet the anion of benzoic acid, a toluic, phenylacetic acid, the butyl-benzoic acid.

Preferred A are anions of aliphatic carboxylic acids with 2 to 8 carbon atoms, for example the acetate ion or aeions more aromatic. Carboxylic acids with 7 or 8

Carbon atoms, for example the benzoate ion.

Suitable carrier materials for the new compounds are polyamides and copolyamides, which are obtained by polymerization from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams. the Substrates can be in the form of threads, bristles, foils, injection molded articles, etc.

The compounds of the formula I are added to the carrier materials in an amount which, based on the carrier material, Corresponds to 1.0 to 500 ppm manganese. Manganese additives of 10 to 200 ppm are preferred, particularly preferred 10 to 70 ppm, based on the carrier material.

The incorporation of the new connections "" itt the ■ poly, amide can take place before, during or after the polycondensation, if appropriate together with other »additives. As such come into question:

Pigments, mainly titanium dioxide in both of them

3098U / 1234

BATH ORIGINAL

Modifications of rutile and anatase in concentrations of 0.01 3.07o, but also colored pigments such as cadmium sulfides, phthalocyanines, Perylene pigments; Chain regulators such as acetic acid and benzoic acid; Phenol or arain antioxidants such as 1,3,5-trimethyl-2,4,6-tri- (3,5-di-tert-butyl-4-hydroxy-benzyl) benzene, Pentaerythritol [3- (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid "] tetraester, 1,6-hexaraethylene- | _3- (4-hydroxy-3,5-di ~ tert -butylphenyl) propionic acid] diamide, 4,4'-butylidene-bis (3-methyl-6-tert.-buty! Phenol), Ditert.-octyl-diphenylamine, UV absorber, which is preferably incorporated into the polymer after the polycondensation e.g. 2- (2'-hydroxy-3 ', 5'-di-tert-amyl-phenyl) -benzotriazole and 2- (2'-hydroxy-5'-methyl-phenyl) -benzotriazole; other additives such as antistatic agents and flame retardants.

The new compounds can also be added to the finished polyamide before or during molding, for example by breading ("dry blending") on dried granules or by applying a solution of the inventive Compounds and optionally other additives on the polyamide and subsequent evaporation of the solvent.

Various processes are suitable for the preparation of the compounds of the formula I. For example, 1 or 2 moles of a compound of formula II

0 nil «

t / ²

R ₁ -P (II)

ONa
3098U / 1234 BAD ORIGINAL

in which R and R ″ have the meanings given under formula I. have with 1 mole of a compound of formula III

Μη ⁺⁺ (Α ^Θ ) _. (III)

wherein A has the meaning given under formula I, implement.

But you can also use 2 moles of a phosphonic acid half-ester the formula Ha

"OH

wherein R, and Rp have the meanings given under formula I.

with 1 mole of manganese (II) carbonate or manganese (II) hydroxide.

Solvents are suitable for these reactions especially water, alcohols, especially methanol, ethanol and Isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Dioxane, tetrahydrofuran, acetonitrile and mixtures of these solvents.

Since the manganese (£ I) ion is easily oxidized, it is possible to glow di.v. Conversion advantageous in an inert gas atmosphere,

the 2.11. may consist of nitrogen by.

Since the manufacturing processes described are

If equilibrium reactions are involved, those formed fall

3098U / 1234

BATH ORIGINAL

Compounds often as mixtures of the. desired Compounds of the formula I more with these Im concerned Reactlonsmedimtm Contains compounds in equilibrium.

Such mixtures obtained by the production processes described are also suitable as light stabilizers for polyamides.

The invention is explained in more detail in the following examples.

3098U / 123 * BAD ORIGINAL

Examples 1 to 5 (see Table 1)

0.1 mol of the phosphonic acid half-esters isolated as sodium salts from column 2 and 9.90 g. {0.05 mol) manganese (II) chloride tetrahydrate are dissolved in 400 ml of boiling ethanol. Sodium chloride precipitates out and is filtered off. In example 5, the manganese salt of the half-ester also partially precipitates at the same time. In this case, the sodium chloride is not separated off and the suspension continues to be used. The Piltrat respectively. the suspension obtained is evaporated to dryness and the residue is extracted with the solvent mentioned in column>. The evaporated extract is then the in column ¹ l
subjected to further cleaning described and then at a temperature of 6O ⁰ C and a pressure of 11 mm Hg during
Dried for 8 hours. According to this procedure, the manganese (II) salts mentioned in column 5 and their properties are obtained
in columns 9 to 10 are described.

309814/1234

Table I.

2
Starting
product 0
I.
P-ONa 3
Extraction
middle K
additional
Cleaning ope-,
ration 5
End product
Mn (II) - 6th 7th 8 9
properties Colour-
Consol
stence * 10 -ONa
C ₂ H ₅ Ethanol Solve in Methy-r
lene chloride and
Failures with
Ether Bis- (O-ethyl-
ethylphospho-
nat) Geha
w _t
P. It
Mn the substance
is soluble in
(h in the you
heat
k b. Clear emu,) weak
pink -
powder Enamel
Point
(OC) O
• ^ c CK- 0
! ^D.
\
CH- 0 chloroform Extraction with
acetone 3is- (0-ethyl-
isopropyl-:.
phosphonate) 18.2 16.6 Water (k)
Ethanol (fc)
Ligroin (h) White -
powder
T 79 - 80 ° _i.
ν. 0
It
i>
* chloroform Extraction with
absolute
Ethanol * To- (0-n-bu-
tylcyclohexyl-
phosphonate) I7.4 15,> Water (k)
Ethanol (h)
Toluene (h) weak
beige -
Powder. > 340 °
(Decomposition)
NJ
ro 13.2 11.2
r. · Ethanol (k)
Chloroform (k)
Toluene (h) ISJ
tn
> 250 °
(Decomposition)

Example 4 to 10 (see Table II)

0.1 mole of isolated as sodium salts phosphonic column 2 are dissolved in the time specified in column 3 on the type and amount of solvent and at 25 to 30 ⁰ C a solution of 10.2 g (0.0515 mole) of manganese (II) chloride tetra ~ hydrate in 50 ml of the same solvent was added dropwise. The resulting precipitate is sucked off and washed out with the solvent mentioned until no more chloride ions can be detected in the piltrate. (Example 5 behaves differently in this work-up stage. When the manganese salt is added, instead of a solid precipitate
an emulsion, which is extracted with ether. After this solution has been dried with sodium sulphate, the ether is evaporated off and the residue is worked up further, as can be seen from the table). The crude manganese (II) salts isolated in this way are, in some cases, subjected to a further purification, which is described in column 4. The products are then heated at 60 C and a pressure of 11 mm Hg for 8
Hours dried. According to this procedure, the manganese (II) salts mentioned in column 5, the properties of which are described in columns 6 to 10, are obtained.

0 9 B U / Ϊ 21 4

BATH ORIGINAL

t
1 2
Starting product 3 I. 4 Table II 5 End product
Mn (II) - 6 7 ..._ 8 9 10 t (%)
Kn Properties
the substance is
soluble in
(towards the boiling point
k at room temperature) Colour-
i consi
stence Enamel
point (OC) example
Mon O
11
C _n H ₁ . P -ONa
8 I 'j
OCzH ₅ ί
ι
solvent
flenge in () additional cleaning operation Bis- (O-ethyl-n-
octyl phosphonate). Salary
P. 11.1 Dimethylformamide (k)
Chloroform (k) weak
pink -
powder fO
N>
. a * 3, : ί
i 0
CH ₇ (CHJ. CH-J-ONa.
^{3 Z3} i CO ₉
^C 2'O Water ;
(70 ml) no Bis- (0-n-butyl-2-ethyl-
hexylphosphonate) 9.9 Chloroform (k)
Ligroin (k) White -
sticky
Dimensions ' cr> ^
he* 5
U)
O water
(300 ml) Extraction with ethanol at
Room temperature Bis (0-ethyl-n-dodecyl-
phosophonate) 9.2 Water (h)
Chloroform (h)
Ligroi η (h) weak
pink -
powder 76-7 ¹ ? "' L co— 1
OO
>% ^0C 4 ^H S Water.
(70 ml) Recrystallization from ethanol Bis- (0-n-butyl-octa-
decylphosphonate) 10.2 6.65 Dimethylformamide (h)
Ethanol (h) '
Ligroin (h) White -
powder 98-99 ⁹ , α>
** 7 β \ - ^. ONa
^w Shi lOJiges Aetha
nol (120 ffil) none ■ Bis- (0-n-octadecyl-
phosphonate) 6.3 Dimethyl formamide Ch)
ToIuq) (k) weak
pink -
powder 118-120 ° 8th O
f ^ —CH-Ρ— ONa 20?
Ethanol
(150 ml) no Bi s- (O-ethyl-benzyl -
phosphbonate) 10.9 Dimethylformamide (h) weak
pink -
powder 200-204 ° 9
»Ρ CH-P-ONa
² OC ₇ H / water
(150 nl) no Bi s- (O-ethyl-a-naphthyl -
phosphonate)
I. 10.0 Dimethylformamide (h) White:-
powder 228-229 ° )
j
;! 10
ρ
I. Ethanol
(470 nl) no 11.1

Example II '■.

50 ppm of Mn as Mn-PhOßphonat of Example 1, 2/6/8 or 9 were dry-coated on dried Polyarald-6 granules, matted with 1.8 # (anatase), and the breading mixture was added to 20 of the monofilaments via Esc truder spun and then stretches irers.
For dip Yerglelchs formulation the 50 ppm Mn would correspond-

End amount of Mn-IZ-aoetat dissolved in water and this solution on highly patted polyamide-6 granulate (1.8 ^ TiOg) equally dried up. The dry breading mixture was then also spun through an extruder to form the monofilaments and drawn.

As a further comparison, Mn-free monofilament silk matted with 1.8ji TiO 2 was also produced.

These 7 silk formulations were placed on a white cardboard background exposed tension-free in the Xenotest- ^ 50, and after 500, 1000 »1500 and 2000 hours exposure time the mechanical Strengths determined. Obtained values see table III,

3098U / 1234

Table III

additions
* / % Residual strength after hours (hours)
Exposure time 1000 (hrs) 1500 (hrs) 2000 (St.d) without Mn 500 (hrs) - - - 50 ppm Mn as Mn-
Phosphonate from Ex. 1 20 β 80 fo. 70 %. 60 fo 50 ppm Mn as Mn-
Phosphonate from Ex. 2 90 % 85 fo 70 % 65 % 50 ppm Mn as Mn-
Phosphonate from Ex. 6th
» 85 % Ib fo 65-Si 55 % 50 ppm Mn as Mn-
Phosphonate from Ex. 8 85 * " 70 % 6 <yfi 50 % ■ 50 ppm Mn as Mn-
Phosphonate from Ex. 9 85 % 85 fo 75 % 65 % 50 ppm Mn as
Mn II ace did 95 % ' 65 fo 40. % - 80 %

3 0 9 * 8 14 / 1.2 3 A

Claims (1)

Claims in which R, alkyl with 1 to 18 carbon atoms, cyclohexyl, unsubstituted or substituted by 1 or 2 methyl groups aryl with 6 to 10 carbon atoms or aralkyl with 7 to 11 carbon atoms, A the anion of an aliphatic Carboxylic acid with 1 to 18 carbon atoms or an aromatic carboxylic acid with 7 to 11 carbon atoms or that Chlorine, bromine or iodine anion, χ 1 or 2, y 0 or 1, vzobei χ + y is 2 and R ^ is alkyl of 1 to 18 carbon atoms mean. 2. Compounds according to claim 1, characterized in that that R-, alkyl with 1 to 18 carbon atoms, cyclohexyl, Mean phenyl, benzyl or naphthylmethyl. 3. Compounds according to claim 1, characterized in that that R-. Alkyl of 1 to 12 carbon atoms, phenyl or benzyl. 3098U / 1234 - ■ 15 ■ 4. Compounds according to claim 1 “characterized” in that R 1 is alkyl having 2 to 12 carbon atoms, phenyl or benzyl and R _{2 is} alkyl having 2 to 18 carbon atoms. 5 »" Compounds according to claim 1 »characterized in that R, alkyl with 3 to 12 carbon atoms or benzyl. 6. Compounds according to claim 1, characterized in that A is the anion of an aliphatic carboxylic acid with 2 to 8 carbon atoms, the anion of an aromatic carboxylic acid with 7 or 8 carbon atoms, the chlorine, bromine or iodine anion, and Pv ₂ methyl, Mean ethyl, propy, butyl or octyl. 7. Compounds according to claim 1, characterized in that A is the anion of acetic or stearic acid or the chlorine or iodine anion, and R «is methyl, ethyl or butyl mean, 8. Compounds according to claim _t, characterized in that χ 2 and y are 0. 9. Compound according to claim 1, of the formula C ₂ H ₅ -P _n ^ Mif 309814/123 * - 16 - Compound according to claim, of the formula CH CH. CH-P Mn Compound according to claim 1 of the formula ^C 12 ^H 25 ~ ^P .0 Mn Compound according to claim 1 of the formula O OC ₁₈ H ₅₇ Mn Compound according to claim 1 of formula 0 I If T. H .Mn ^C l8 ^H 37 Compound according to claim 1 of formula 0. OCU ^ Mn '2 15 · Use of compounds of claim 1 for Stabilizing polyamides. 3098U / 123A - .17 - 16 ·, use according to claim 15, characterized in that that is stabilized with compounds of claim 2. 17, use according to claim 15 j, characterized in that that is stabilized with compounds of claim 3. 18th Use according to claim 15, characterized in that, that with compounds of claim 4 is stabilized. ^ q. Use according to claim 15 , characterized in that with compounds of claim 5 is stabilized. 20. Use according to claim 15, characterized in that, that is stabilized with compounds of claim 6. 21- - Use according to claim 15 * characterized in that that with compounds of claim 7 stabilized will, 22- Use according to claim 15 * characterized in that that with compounds of claim 8 Stabilizer becomes. 303814/123 * BATH ORIGINAL