DE2153159A1 - ANTI-ELECTROSTATIC MOLDS AND MOLDED BODIES MADE OF POLYOLEFINES - Google Patents

Description

CHEMISCHE WERKE HÜLS AG 4370 Marl, October 20, 1971

- Patent Department - 2068 / U

Our sign; OZ 2587

Antielektrostati see molding compounds • and moldings made from polyolefins

The invention relates to antistatic molding compositions and molded articles made from polyolefins with additives containing nitrogen Links.

Plastic parts made from polyolefins tend to be known to contribute Storage and use due to electrostatic charges attract dust to a large extent, which makes their utility value considerable is decreased.

Various means have been proposed to avoid these difficulties. So you can see the surfaces of Coating polyolefin objects with a mass that the reduces electrostatic charge. However, such methods usually have the disadvantage that the effectiveness is lost, as soon as the anti-static coating is removed through use or cleaning. Longer lasting effect is achieved if the antistatic additive is incorporated into the polymeric material and molded parts from these mixtures manufactures. These additives include, for example, quaternary ammonium salts, polyalkylene glycols and polyalkylene glycol esters.

They already have even better properties, for example proposed oxethylates of alkanols and alkylarylphenols (BE-PS 536 623 and GB-PS 731 728), but these compounds tend for exuding if you incorporate the necessary amount into the plastic for a sufficient effect. 53/71

309818/1112

20th to 1971

A further increase in the anti-electrostatic effect can be achieved with nitrogen-containing compounds, such as amides and aminocarboxylic acid derivatives (FR-PS 1 377 803-8), oxazolines and, to an even greater extent, with alkylamines (BE-PS 655 182 and 655 183), in particular with oxethylates of alkylamines (DE-PS 6k-5 800, FR-PS 1 3 ^ 5 827 and 1 322 626, DT-AS '1 228 05O), in which the Bls-hydroxyethyl derivatives are the most effective. However, these compounds often have the property that in the first days after producing the molding, the formation of a surface film is still too low, so that ψ the additive does not immediately take full effect. However, this has the consequence that the processing. E.g. mold separation during ^: injection molding, occurring, generally very high electrostatic charge cannot flow away immediately, so that within a few days the moldings become unsightly due to the attraction of dust, all the more so because the dust supply in fäbrikationsstätten due to the hard-to-avoid turbulence in general is very big.

A large number of the cyclic compounds are described in the patent literature as alkyl imidazolines and tetrahydropyrimidines described as highly effective, of which the latter are particularly effective k on the surface of fittings. this leads to however, very often to the undesirable formation of deposits.

The task was therefore to make polyolefins antistatic equip and use the advantages of the amines and cyclic amine amides without the disadvantages outlined above the to spade. Effectiveness and the formation of deposits have to be accepted.

According to the invention, this object is achieved in a surprising manner by using compounds of the formula:

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O.Z. 258? 2Ö ~ 10.1971

1 2

where R and R are hydrogen, an aliphatic, cycloaliphatic or optionally substituted aromatic radical with 1 to 25 carbon atoms, R also a radical (c H _p θ) H, χ ~ 2 or 3 and η = 1 to 10, R and R hydrogen , aromatic or aliphatic ^ radicals with 1 to 25 carbon atoms, which also

3 can be linked to form a cycloaliphatic ring, and R also an alkoxymethylene or aryloxymethylene group with 2 to 26 carbon atoms, with at least one of the radicals

1 2 - 3 Ii
R, R, R or R is an alkyl or alkylene radical of at least 6 carbon atoms, optionally as quaternary salts or together with up to equivalent amounts of organic or inorganic acids.

The compounds of the formula shown are 7-0xa-1,5-diazabic3 ^r clo / ^ «3 .θ / nonane, which can be 5, 6, 8, 9-substituted and are structured as follows:

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ο.ζ.

20.10, 197

Suitable anti-static equipments due to the additives Polyolefins are e.g. high and low pressure polymers, made of ethylene, propylene, butene ~ (i), pentene (l) visw., In particular all types of polyethylene with molecular weights between 20,000 and 150,000, polypropylenes with molecular weights between 100,000 and 800,000, polybutenes- (1) with molecular weights between 300,000 and 3,000,000, polypentene- (1), and mixed polymers and polymer blends thereof.

Preference is given to those polyolefins as can be obtained by means of low-pressure processes, in particular according to Ziegler and Natta, is obtained, especially using mixed catalysts made from titanium compounds such as titanium tri- and tetrachloride or halogenated titanium acid alkyl esters on the one hand and from organoaluminum compounds such as aluminum trialkylene, aluminum alkyl halides and sesquichlorides on the other hand.

The use of the claimed compounds is to be understood as meaning, on the one hand, their application to the surfaces of the moldings (for example by dipping or spraying on the compound dissolved if desired in water or organic solvents) and, on the other hand, the incorporation of 0.01 to 2.0 percent by weight, based on the molding compositions of the compounds. As molding compositions and moldings are in this case injection molding _t extrusion and deep drawing the body, as well as to understand films, threads and fibers.

Suitable compounds are, for example, 8.9 ~ Dioiethyl-6-nonyl-5-dodecyl-7-oxa-1 , 5-diaz; a-bicyclo / ^. 3 .O / nonane, 8-phenoxy methyl 1-6-ethyl-5-octadecenyl-7-oxa-1,5-diaza-bicyclo / 2j..3.O / nonane, 8-butoxyraethyl-6-propyl-5-cyclodec3'-l ~ 7-oxa-1,5-diaza-bic3'-clo

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Particularly suitable 7-0xa-1,5-diaza-bicyclo / i-.3.Ojnonane der claimed type are those in which R is an alkyl or Alkeöyigruppe with 6 to 25, preferably 8 to 18, in particular 10 to 14 carbon atoms, R is hydrogen or an alkyl or alkenyl group with 1 to 5 »preferably 1 and 2 carbon

3 ·

atoms, R is hydrogen or an alkyl or alkenyl group

1 to 5 »preferably 1 to 2 carbon atoms, or an alkoxy

methyl group with 2 to 6, preferably 2 to 3 carbon atoms,

4 ·

R is an alkyl or alkenyl group with 1 to 5, preferably 1 to

2 carbon atoms, or preferably hydrogen.

Examples of suitable groups R are n-hexyl, n-octyl, trimethylhexyl, n-nonyl, n-decyl, n-decenyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-Hexadecyl, n-Octadecenyl and n-Octadecyl radical. Preference is given to the n-decyl, n-undecenyl, n-undecyl, n-dodecyl, n-tridecyl, _t i-tridecyl, n-tetradecyl radical or mixtures thereof, such as, for example, the mixture of C _1n - to C ^ -Alkyl residues.

2
The group R which can be used is, for example, hydrogen or the methyl, ethyl, propyl, n-butyl, i-butyl, butenyl, n-pentyl radical. The methyl and ethyl radicals are preferred.

• '

3.
The group R which can be used is, for example, hydrogen or the methyl, ethyl or methoxymethyl and propoxymethyl radicals. The methyl and methoxymethyl radicals are preferred. "

k
The group R which can be used is, for example, hydrogen or the methyl, ethyl and n-butyl radicals. Hydrogen is preferred.

Particularly suitable compounds are, for example, 8-methyl-6-ethyl-5-dodecyl-7-oxa-1,5-diaza-bicyclo / ^. 3.O / nonane, 8-methoxymethyl-6-methyl-5-tetradecyl-7-oxa-1, S-

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10/20/1971

Particularly suitable 7-0 ^ a-1 »5 ~ ⁽ iiaza-bicyclo / 4.3.o7nonane der

1 2

claimed type are also those in which R and R are hydrogen or an alkyl or alkenyl group with 1 to 5 » he-

preferably 1 to 2 carbon atoms, R an alkyl or alkenyl group with 6 to 25 »preferably 8 to 16, especially 9 to 13 carbon atoms or an alkoxymethyl group with 7 to 26, preferably 9 to 19, in particular 11 to 15 carbon atoms,

if '

R is an alkyl or alkenyl group with 1 to 5 »preferably 1 to

2 carbon atoms or preferably hydrogen.

12th
The methyl, n-propyl, η-butyl, i-butyl, n-pentyl and n-pentenyl radicals, for example, can be used as groups R and R. The methyl and ethyl radicals are preferred.

3 '

The group R which can be used is, for example, the decyl, hexadecyl, dodecylbxymethyl radical or mixtures, such as, for example, the mixture of C _Q - to G _1? —Alkyl radicals.

k
The group R which can be used is, for example, hydrogen or the methyl, ethyl and butenyl radicals. Hydrogen is preferred. Particularly suitable compounds are, for example, 5.8.9-trimethyl-6-dodecyl-7-oxa-1 .S-diaza-bicyclo / Zi ^ .O / rtonan, S-dodecyloxymethyl-o-ethyl ^ -iaethyl-T-oxa-i .5-diaza-bicyclo- / Ji * 3. Ö / nonaxi and 5-8-diethyl-6-hexadecyl-7-oxa-1 .5-diaza-bicyclo-A.3.o7nonan.

Very particularly suitable 7-oxa-1,5-diaza-bicy cXofh » 3 · O / nonanes of the claimed type are those in which R is either hydrogen or an alkyl or alkenyl group with 1 to 25» preferably 1 to 6, in particular 1 to 2 carbon atoms, R is an alkyl or alkenyl group with 5 to 25, preferably 7 to 17 »

3 in particular 9 to 13 carbon atoms, R is hydrogen or an alkyl or alkenyl group with 1 to 25 »preferably 1 to 5, especially 1 to 2 carbon atoms or alkoxymethyl groups

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with 2 to 26, preferably 2 to 6, especially 2 to 3 carbon atoms, Ii hydrogen or an alkyl or alkenyl group with 1 to 25, preferably 1 to 5, in particular 1 to 2 carbon atoms or are preferably hydrogen.

As a group R can be used, for example, the methyl, ethyl, n-propyl, η-butyl, i-butyl, buten'yl radical, are preferred the methyl and the ethyl radical.

Examples of suitable group E are n-heptyl, n-octyl, trimethylpentyl, n-nonyl, n-X-indecyl, n-undecenyl, i-tridecyl, n-tetradecyl, n-pentadecyl , n-heptadecenyl and n-heptadecyl "Preference is given to the n-nonyl, n-DEC3 ^r l, n-undecenyl, n-TJndecyl-, n-dodecyl, n-tridecyl, i-tridecyl, or mixtures of these, such as, for example, the basic structure of C _Q - to C ₁ _ -alkyl residues,

As a group R are, for example, hydrogen or the methyl, butenyl or methoxymethyl and propoxymethyl radicals, The methyl and methoxymethyl radicals are preferred.

As a group R are, for example, hydrogen or the methyl, ethyl and propyl radicals. Hydrogen is preferred.

Very particularly suitable compounds are, for example, 5 »8-dimethyl-i. 6-tridecyl-7-oxa-1.5-diaza-bicyclo / i.3.07 nonane, 8-methyl-6-undecyl-5-ethyl-7-oxa-1. 5.dia ^z a— bicyclo ^ 7f.3 .O / nonane.

The 7-0xa-1.5-diaza-bicyclo / i.3 «07nonanes with 2 long alkyl or alkenyl groups (C _g to C) are also suitable for special areas of application, especially where the substances should have low water solubility, such as to the external

309818/1 112

10/20/1971

And internal equipment. By Pasern. Here are the connections with the two long alkyl groups in 6.9- »6.8- and 5 * 6-positions better than those in the 8.9- »5'· 9 and 5« 8 positions. Suitable Compounds are, for example, 8-decyl-6-undecyl-5-niet] iyi-7-oxa-1 . 5-diaza-bicyclo / 7 + »3» o7nonane, S-methyl-o-noriyl ^ -dodecyl ^ - oxa-1,5-diaza-bicyclo / ^, 3 «0 / nonane, 9-octyl-6-undecyl-5-ethyl-7-oxa-1 .5 - '/ i7

7-0xa-1 .5-aiaza-b "icyc'io / ^ '« 3' Ojnonanes with alkyl or alkenyl radicals longer than 2 are somewhat less effective. Such 7-0xa-1 are almost completely ineffective 5- * diaza-bicyclo / 2j..3.Ci7 nonanes which do not contain at least one alkyl or alkenyl radical with at least 6 carbon atoms.

The claimed bicyclononanes can also be used as quaternary salts, e.g. as reaction products with chloroacetic acid and its alkali salts or chlorohydrin or alkyl halide, or as salts with acids, e.g. with mono- and dicarboxylic acids, such as acetic acid, lauric acid, oleic acid, oxalic acid, tartaric acid, succinic acid or dodecanedioic acid. (1.12) and / or with hydroxycarboxylic acids such as lactic acid, G-lykolsaure or ricinoleic acid or phosphoric acid or its Partialalkylestern or with sulphonic acids such as alkane- or _1ς C C _-, p-alky benzenesulfonic acids are used.

The salts can be produced, for example, by doing the Mixture of equimolar amounts of one or more bicyclo / ^. 3 »07 nonane and one or more acids, optionally in the ¥ ärrae, transformed into a homogeneous melt by intensive stirring; and then allowed to cool, or both components takes up in suitable solvents and the combined solutions evaporates to dryness, which largely eliminates the risk of possible discoloration.

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The amounts of the above-mentioned antistatic agents incorporated into the polyolefins are expediently between 0.01 and 2.0 percent by weight, based on the polyolefin. Amounts between 0.1 and 0.75 percent by weight are preferred. Concentrations higher than 2.0 ^c ß> are usually not necessary as they do not bring about any improvement.

• You can add the new additives to the polyolefin in various ways bring in. For example, you can "use the polyolefin the anti-static agent directly in a mixer transform into a homogeneous mass. In general, any commercial high-speed mixer is suitable for this purpose. One can also First, mix a higher than the desired percentage of the anti-static agent into the polyolefin and Then bring this mixture to the desired antistatic content by mixing in more polyolefin. The antistatic agent can also be dissolved, dispersed or suspended in a suitable organic solvent or emulsify and add the solution, dispersion, suspension or emulsion to the polyolefin powder and stir thoroughly. The solvent can then be removed, for example, by distillation. A well-suited solvent for these purposes is for example methanol. But all other easily distillable solvents are also suitable for this purpose. The antistatic agent can also be incorporated into the polyolefin, e.g. directly on the salt or perform during injection molding in an extruder.

The method, initially an anti-static agent, has also proven its worth to produce highly concentrated granules and this during processing by mixing in additive-free granules to bring to the desired level of antistatic.

309818/1112

10/20/197T

You can use additional ones that are otherwise common in plastics processing Add additives, e.g. dyes, stabilizers, plasticizers, extenders and fillers, as well as lubricants.

For example, it can be useful to add additional substances to the polyolefin which prevent the antistatic agents from turning slightly yellow after prolonged exposure to high temperatures. Suitable stabilizers of this type are, for example, phosphites, in particular didecylphenylphosphite, decyldiphenylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (nonylphenol + 9 mol ethylene oxide) phosphite, which in amounts of 0.01 up to 0 _t h percent by weight, based on the polyolefin, can be added. The addition of alkanesulfonates, for example sodium pentadecanesulfonate, has the same beneficial effect. This requires about 0.05 to 1.0 percent by weight, based on the polyolefin.

The anti-static behavior of the moldings is through the ash dust test method, through information on the dustiness of the test specimens a) in a normal atmosphere (normal dustiness) , b) when spraying with a fly ash / soot mixture and c) when sprinkling with a special powder (color powder test) subject, checked. These tests are carried out on test cups (42 χ 25O χ 320 mm).

Another test * carried out on injection molded panels (k 65 χ 120 mm) consists of measuring the electrical surface resistance according to DIN 53 ^ 82. The ash dust test is carried out as follows: The test specimen is rubbed vigorously 10 times with fresh cellulose and held 0.5 cm above fresh, crushed cigar ash. The test is considered positive if the test body does not attract any ash particles (sign +, i.e. it relates to the effect of the incorporated

309818/1112

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■ ^L ; ^? n ..- '-20.10.1971

Substance). Furthermore, the signs (+) = low, {+ -) = meanV (^) = stronger and - = stronger ash attraction ·. Of the The test is carried out 1 and 8 days after the test specimens have been produced.

When observing the so-called normal dusting takes place the division - also semi-quantitative - into none (k), very easy (si), easy (l), medium (rn), strong (st) and very starch (sst) dustiness, observed 8 days after manufacture. Figures from Lichtenberg are marked with *.

The so-called dust test consists in that the test specimens

1 day after production in a chamber made from a solids nozzle sprayed with a mixture of $ 75 fly ash and $ 25 soot -will. The classification is the same as for normal dusting.

The so-called colored powder test, carried out Ϊ and 8 days after Production of the molded body is the test of how strong the two components of a mixture of red-colored sulfur bloom are and blue colored bear moss spores of different Places on the plastic surface are attracted (red places = areas of positive charge, blue "places = areas negative charge on the plastic surface).

In the examples PE means a polyethylene with a density of 0.900, the average molecular weight of 52,000 and the reduced viscosity of 1.5, PP a polypropylene with the density ^; of Ö.9O6, the average molecular weight "" of '^ 70,000 and the reduced viscosity of h and PB a ■ "polybutene- (l ·) with the density of 0.910, the average molecular weight of

2,000,000 and the * reduced viscosity of h, - ■ · ■

As can be seen from the 28 examples and comparative examples shown in the table, those bicyclononanes am best that contain a long alkyl group. Of these

30981871 112

again those are best in which the long alkyl »

group is in the 6-position (R ", Examples 6, 7, 20 and 27). Also effective are the compounds in which the long alkyl group is in the 5-position (R, Examples 4, 5, 19 and 26) _$

/ 3 4

followed by the 8 and 9 positions (R and R, Beisj) iele 8, 9

and 21 and 11).

The effect of the compounds with 2 long alkyl groups is somewhat less than that of those with one group. In their case, the 1,2- and 2,3-long alkyl-substituted radicals (Examples T2 and 22 as well as 13 and 23) are better than the 1,3- "and 1,4-long-alkyl-substituted radicals R. The compounds with 3 long alkyl chains (Examples 16 Compounds with only short alkyl chains (Comparative _{Examples 2, S} 3 and 18) are even less effective. It can also be seen that 11 and 12 carbon atoms in the alkyl group produce the optimum (Examples 4 and 6 versus 5 and 7)

3 0 9 8 18/1112 säD ORIGINAL-

O.Z. 2587

Poly Parts additions R ¹ _p 2 I ⁴ • CH ₃ Tabel R ⁴ Ash test 8th normal dust Color powder 1 8th sst, * SST * * * sst, * k sst; ^ 20 January D.197 1 I. Surface resistance [Mi3 LF j
8th C and r. LF
8th : · Ιο 7th 7-10 > ιο ⁷ IMO > ΐο ⁷ 8MO ole to 300 I ³ CH ₂ OCH ₅
^CH 3
^CH 3 ampl. test test after production of the test specimen sst, * - sst, * sst, ^ e 1
1 SSt ^ at 23 ^c 40%
ι I Days after manufacture 3 · 10 ⁴
3.3Ο ⁴ > ιο ⁷ 1 · 3Ο ⁴
7MO > ιο ⁷ 5MO ⁴
χ. ίο ⁵ > 2Ο ⁷ 2MO ⁴
8 · 2Ο ⁴ at fin Parts
Poly CH CH H 3 8th sst.-lff
si
1 SSt, *
si
1 SSt, *
1
1 m, sst, * f
si
1 60% r.
ι I 6MO ⁴ > ιο ⁷
6 ³
ι · ιο ⁴ ι · ίο ⁴ > ιο ⁷
7.1O ⁴ 2MO ⁵ > ιο ⁷
3.1O ⁴
7MO ⁴ ι. ίο ⁵ game- olefin R * ^R ο
^C 2 ^H 5
13 25
^C 38 ^H 37 ^C 2 «5
^CH 3
^C 2 ^H 5 R ^{3 CH} 3 ^CH 3
^CH 3
H Days • 1 \ 7
MO 3-3O ⁴ 2 7-ΙΟ ³ 4th 9MO ⁴ 3 6-ΙΟ ⁴ No. ^C 2 ^H 5 k k ra
m k > io ⁷ 5 3 ⁴
2 · 10 ⁵ ι · ιο ⁴
9 3 ⁴ 2- ΙΟ ⁵
7 · 10 ⁵ 7-10 ⁴
2 · 10 ⁵ PE ^V) 0 ^C 2 ^H 5 ^C 31 ^H 23 ^C 3 6 ^H 33 H f \ \
\ *) 1
1 1
1 m 1
1 > io ⁷
8-10 ³
4MO ⁴ 4 ΊΟ ⁵ i-io ⁵
G 9-ΙΟ ⁵
G 4 · 10 ⁵ PE ^V) 0.5-2.0 ^CH 3
^C 2 ^H 5 ^C 3 7 ^H 33
CH ₃ CH ₂ OC ₇₂ H ₂₅ H
H - . 1 1 ' St.
St. 1 3 2 3Ο ⁶
5 3 ⁶ 1 · 10
3.3Ο ⁶ G-IO
> ιο ⁷ 3 · 10 ⁶
· 5 · ΙΟ ⁶ ! _PE v) ■
PU
PE 0.5-2.0
0.5
0.5 ^CH 3 ^c 5 ^H n CH ₃
^CH 3 H + 1 1 St.
sst, f- 1 > ιο ⁷ 5 ΊΟ
> ιο ⁷ > ιο ⁷ > ιο ⁷
> ιο ⁷ 2 ^C 4 ^H 9 CH ₃ ^C 10 ^H 21 H (4) 1
1 1
m sst, Kr 1
1 > ιο ⁷ > ιο ⁷ > ιο ⁷ no ⁷ 3
4th
5 PE 0.5 ^CH 3
^C 3 2 ^H 25 ^C 2 ^H 5
^C 9 ^H 17 ^C 32 ^H 25
^CH 3 ^C 8 ^H 17
H (+) (+ -) 1 tn m PE
PE 0.5
0.5 ^C 2 ^H 5 ^C 11 ^H 23 ^C 10 ^H 21 H (t) m
m ra
m m
m 6th PE 0.5 30 23
^C 12 ^H 25 ^C 2 ^H 5 ^CH 3. H
^C 8 ^H 37 <-> ! Π St.
sst, # m
sst, & St.
sst * 7th
8th PE 0.5 ^C 12 ^H 25 ^C 9 ^H 19 H (4-) SSt, * sst, * ¹ SSt f- 9 PE
PE 0.5
0.5. ^C 4 ^H 9 ^C 2 ^H 5 H C-) C-) 20th PE 0.5 <-) Ϊ1 ■
12th PE
PE 0.5
0.5 -. - 13th PE
ppV) 0.5
0 ψ » 24
15th pp ^v) 0.5-2.0 - 16
17th 18th

OZ, 2587 October 20, 1971

co ο co

at Poly Parts additions R ¹ Pp i R ³ R ⁴ Ash test 8th normal dust Color powder 1 8th Surface resistance [MfI] ". LF j 40% r. LF ng game - ole on IOC ^C 12 ^H 25 ^CH 3 H after ampl. test test - test c .body at 23 ⁰ C and 8 I. ι I 8th No. fin Parts ^C 2 ^H 5
^C 2 ^H 5 R ^ ^{K CH} 3 H
H 60% 3 laugh Hey rstelli. I.
i-io ⁵ !
4 ' Poly N- ^C 32 ^H 25 R ^{2 CH} 3 H 1 8th τη 1 ¹ I. 8 · 20]
2-10 ⁵ j olefin R ¹ CH ₃ ^C 2 ^H 5 ^C 16 ^H 33 H Days f
(■ (-) Manufacturer] .ung dei 1
m 1
1 Days r 2-10 ⁴
• 3 5 ■ 1O ⁵ 9-10 ^; ^C 12 ^H 25 ^C U ^H 23
^C 2 ^H 5 ^C 10 ^H 21 H (-) st, * - St. 9.10
6-1Ο ⁴
5 3ΊΟ ⁵
6th 1-10 ° j
6; 19th PP 0.5 ^C 12 ^H 25 ^C 9 ^H 29 ^CH 3 H (-> (~) 1 1 St, * St. 8 -10 ⁴ 3-10 3Ί0
p, 5 .to: 20th
21 PP
PP 0.5
0.5 ^C 2 ^H 5 ^C 11 ^H 23 ^CH 3
^C 14 ^H 29 H
H <-> k
1 k
τη St.
SSt, * St.
SSt, * 3-: o
9-10 ⁴ 4-10
6th 7-10 "
7th Tio ⁵ :
4 ^! 22nd PP 0.5 hsbeisp ^C 9 ^H 19 - (+ -) St. St ₁ ) C 1 1 7-1Ο ⁵
5 I-ICT
MO ⁷ > io ⁷ 6 * io;
3-10 ⁵ 23 PP 0.5 ^C 2 ^H 5 - (t -) St. St. 1
m k
1 9-10
G 9 ΊΟ ³
3 6-1Ο ⁵
5 24
25th PP
PB ^V) 0.5
0 ^C 11 ^H 23
^C 2 ^H 5 _. St.
SSt, #? St.
SSt, * 8-10 '
>! 0 ⁷ 8-10
5 'ΙΟ ¹ 3-10
8-1Ο ⁵ 26th PB 0.5 iel ⁽ "? si si IUl-Ul _ί L-U 7-1Ο ⁴
4th 27
28 PB
PB 0.5,
0.5. C-) k
1 k
1 4-10
i-io ⁵ ν) ₌ Compare L.

_ ι κ - η "7

10/20 T971

Is used in the examples instead of the polyethylene mentioned one with a density of 0.9 ^ 8, a medium one Molecular weight of 130,000 and a reduced viscosity of 3.1 or one having a density of 0.930, an average molecular weight of 1,000,000 and a reduced Has a viscosity of 1.18, raa.n receives comparable results. The same applies when using a polypropylene with a density of 0.905 »the average molecular weight of 3 ^ 0,000 and the reduced Viscosity of 3 or with the density of 0.905 »dem average molecular weight of 600,000 and the reduced viscosity of 5 and when using a polybutene (1) with the Density of 0.910, the average molecular weight of 1,300,000 and the reduced viscosity of 3 or with the density of 0.915 »the average molecular weight of 800,000 and the reduced Viscosity of 2.

It is known from DT-OS 1 952 623 that 7-0xa-1, -5-diaza ~ bicyclo /] ft.3.o7nonane Can serve as intermediates for the manufacture of other compounds, which are called pharmaceuticals and antistatic agents are usable. But not from this to conclude that these bicyclononanes themselves, without further chemical conversion, are outstandingly suitable as antistatic agents. Rather, one had to, for example, from FR-PS-1 582.995 "wo a very similarly built bicycle to achieve a sufficient Effect can only be subjected to a subsequent chemical reaction after incorporation into the polymer must conclude that the claimed bicycles could only be used as intermediates. Also wasn't predict that the bicyclononanes are particularly good antistatic agents for polyolefins.

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Claims (2)

1. Aiitielektrostatische Foi'mmassen and Fonniförper of polyolefins with additives of nitrogen-containing \ ^r erb indungen, characterized by the application of compounds of the formula 12th
where R and R are hydrogen, an aliphatic, cycloaliphatic or optionally substituted aromatic radical up to 25 carbon atoms. R ¹ also has a radical (CH ₀ θ) Η, χ = ^ χ dx. η or 3 and η = 1 to 10, R and R hydrogen, aromatic or aliphatic ^ radicals with 1 to 25 carbon atoms, the can also be linked to form a cycloaliphatic ring, 3 ■ ' and R also denotes an alkoxymethyl or aryloxymethyl group having 2 to 2.6 carbon atoms, at least one of the '■ 1 ρ 3 .... If R, R ~, R or R radicals is an alk} ^r l or alkenyl radical of at least 6 carbon atoms, optionally as quaternary salts or together with up to equivalent amounts of organic or inorganic acids. 2. Antistatic molding compositions and moldings according to claim 1 , marked by a content of 0.01 to 2.0 percent by weight, based on the molding compositions, of compounds of the type claimed. 3 0 9 8 18/1112