DE2153147A1 - ANTI-ELECTROSTATIC MOLDS AND MOLDED BODIES MADE OF POLYOLEFINES - Google Patents

Description

Antistatic 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 are known to have a tendency to contribute Storage and use due to electrostatic charges to a large extent attract dust, increasing their utility value is reduced considerably.

Various means have been suggested to get around this Avoid difficulties. So you can coat the surfaces of polyolefin objects with a mass, which reduces the electrostatic charge. However, such methods usually have the disadvantage that the Effectiveness is lost once the anti-static coating is removed through use or cleaning. More persistent Effect is achieved when the antistatic additive is incorporated into and removed from the polymeric material these mixtures produces molded parts. These additives include, for example, quaternary ammonium salts, polyalkylene glycols and Polyalkylene glycol esters. For example, the already proposed oxethylates of Alkonolen and alkylary! Phenols (BE-PS 536 623, GB-PS 731 728), however, these compounds tend to exude if the amount necessary for sufficient effectiveness is used Incorporated plastic.

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A further increase in the anti-static ■ This can be achieved with nitrogen-containing compounds such as amides and aminocarboxylic acid derivatives (FR-PS 1 377 804-8), oxazolines and to an even greater extent with aminamides (BE-PS 639 449) and alkylamines (BE-PS 655 182 and 655 183), in particular with oxethylates of alkylamines (BE-PS 645 800, FR-PSl 345 827 and 1 322 626, DT-AS 1 228 056), where the bis-hy droxyäthyl derivatives are the most effective antistatic agents are. However, these compounds often have the property that in the first few days after production of the flfc molding, the formation of a surface film is still too low so that the addition does not take full effect immediately. However, this has the consequence that the processing, e.g. Mold separation during injection molding, generally very high electrostatic charges that occur do not flow off immediately can, so that within a few days the moldings become unsightly due to the attraction of dust, even more so than that Dust supply in manufacturing facilities is generally very large due to the difficult-to-avoid dust swirl.

In the patent literature, alkylimidazolines and tetrahydropyrimidines are used (DT-OS 1 544 888, 1 954 291 and 1 962 921), the latter of which surfaced particularly quickly of fittings become effective. However, this sometimes leads to the formation of undesirable deposits.

It is therefore the task of making polyolefins antistatic while taking advantage of the amines and to use cyclic amine amides without the above Having to accept the disadvantages of the late effectiveness and the formation of deposits.

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

R ₁ -NH-GH ₂ -CH ₂ -CH ₂ -Nh-CO-R ₂

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wherein R, an alkyl, alkenyl or cycloalkyl group with up to 26 carbon atoms and R "is an alkyl or alkenyl group with 1 to 5 carbon atoms, optionally together with up to equivalent amounts of organic or inorganic acids.

In a preferred embodiment, the group contains R, 8 to 18, in particular 10 to 14 carbon atoms, the group R ~ 1 up to 3 carbon atoms.

Suitable antielectrostatic by the additions ausrüst- g

Bare polyolefins are e.g. high and low pressure polymers from ethylene, propylene, butene (1), pentene (l) etc., especially all types of polyethylene with molecular weights between 20,000 and 150,000, polypropylenes with molecular weights between 100,000 and 800,000, polybutenes (I) with molecular weights between 300,000 and 3,000,000, polypentene (1) and mixed polymers and polymer mixtures thereof. Preferred are here such polymers as are obtained by means of the low-pressure process, in particular according to Ziegler and Natta, for example using mixed catalysts made from titanium compounds such as titanium tri- and tetrachloride, halogenated titanium acid alkyl esters on the one hand and from aluminum compounds such as aluminum trialkyls, -alkyl halides and -sesqui- { Chlorides on the other hand.

As a group R, for example, the 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 n-decyl, n-undecenyl, n-undecyl, n-dodecyl, n-tridecyl, i-tridecyl, n-tetradecyl radical or mixtures thereof, such as E.g. the structure of C, _- to C, * - alkyl radicals.

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The cyclododecyl, cyclodecyl and cyclohexyl radicals, for example, can also be used.

As a group R ", for example, the methyl, Ethyl, propyl, η-butyl, i-butyl, butenyl, n-pentyl radical. The methyl, ethyl and propyl radicals are preferred.

Using the compounds is the one whose application to the surfaces of the mold body, for example to understand by dipping or spraying the optionally dissolved in water or organic solvents compounds, W on the other hand the incorporation of O.01 to 2.5 wt .-%, based on the Molding compounds, the open-chain aminamides. Shaped bodies are mainly to be understood as meaning injection-molded, extrusion and deep-drawn bodies, as well as films, threads and fibers.

The new additives can be introduced into the polyolefin in various ways. For example, you can use the polyolefin Use the anti-static agent to transform it into a homogeneous mass immediately in a mixer. This is generally done any standard high-speed mixer suitable. You can also first give the polyolefin a higher than the desired one Mix in the percentage of the anti-static agent and then mix in this mixture of additional polyolefin to the desired antistatic content bring. You can also dissolve or disperse the antistatic agent in a suitable organic solvent, suspend 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. One for these purposes a suitable solvent is, for example, methanol. But also all other easily distillable solvents are suitable for this purpose. But you can also

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processing of the antistatic agent into the polyolefin immediately on the roller or e.g. during injection molding in an extruder.

The anti-electrostatic behavior of the moldings is tested using the ash dust test method, through information on the level of dust, the test specimens a) in a normal atmosphere (normal dust) and b) when sprayed with a mixture from fly ash and soot (dust test) and c) when sprinkling with a special powder (color powder test) are tested. These tests are carried out on test trays (42 × 250 × 320 mm).

Another test carried out on splash panels (4 χ 65 χ 120 mm), consists in the electrical surface resistance to be measured according to DIN 53 482. The ash dust test is carried out in the following way:

The test specimen is rubbed vigorously 10 times with fresh cellulose and holds it 0.5 cm above fresh, crushed cigar ash. The test is considered positive if the test specimen does not Attracts ash particles (sign: +, so it refers to the effect of the incorporated substance). Also mean the signs (+) = low ,. (+ -) = medium, (-) = stronger and - = strong ash attraction. The test is carried out 1 and 8 days after the test specimens have been produced.

When observing the so-called normal dustiness, the indentation takes place - also semi-quantitatively - in none (k), very easy (si), easy (1), medium (m), strong (st) and very strong (sst) dustiness, observed 8 days after manufacture. Lichtenberg figures are denoted by.

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The so-called dust test consists in spraying the test specimens with a mixture of 75% fly ash and 25 % soot 1 day after production in a chamber made of a solids nozzle. The classification is the same as for normal dusting.

The so-called colored powder test, carried out 1 and 8 days after production of the moldings, is the test of how strongly the two components of a mixture of red-colored sulfur blossom and blue-colored bear moss spores are attracted to different parts of the plastic surface (rc ⁴ : e places = areas more positive Charging, blue areas = areas of negative charge on the plastic surface).

In the examples, PE means a polyethylene with a density of 0.960, an average molecular weight of 52,000 and reduced viscosity of 1.45, PP a polypropylene with a density of 0.906, the average molecular weight of 480,000 and the reduced viscosity of 4 and PB a polybutene- (1) with the density of 0.910, the average molecular weight of 2 000 000 and the reduced viscosity of 4.

As the table with the 15 examples and comparative examples shows, the optimum effect is in those compounds in which R- contains about 12 carbon atoms (Example 2 to 5) The R, groups in open-chain ones show a particularly good effect Structure (Examples 1, 4, 6 and 9) and as R “the ethyl radical is particularly active.

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Is used in the examples instead of the polyethylene mentioned one which has a density of 0.948, an average molecular weight of 130,000 and a reduced Viscosity of 3.1 or one that has a density of 0.930, an average molecular weight of 1,000,000 and a has a reduced viscosity of 1.18, comparable results are obtained. The same applies when using a polypropylene with a density of 0.905, an average molecular weight of 340,000 and a reduced viscosity of 3 or with a density of 0.905, an average molecular weight of 600,000 and a reduced viscosity of 5 as well as at Use of a polybutene (1) with a density of 0.910, an 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 from 2.

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• L Poly Parts Connection Table the formula R ^{2 C} 2 ^H 5 Ie 8th _ N ^T orraal- dust ssty * Color powder 8th sst, * Surface resistance [ at 23 ⁰ C ίο "
3 10 2 10 • ^LF !
3) 3-30 * and % r
I. . LF
8th 10 °
3 30 ° 10 ίο ³
3 > ^l0 \ 3 i ίο ⁴ ! 10 ³ |
3 ' At-! ole to 100 R ₃ -NH-CH ₂ -CH ₂ -CH ₂ -
NH-CO-R ₀ CH ₃ Ash test e after t ampl. test k test r test specimen k % r ίο ¹⁵
4th later , 2O ⁷ 40
1 position 20th
5 3 , io ^v 10 6th 70 ° I.
4 ί 3 \ ID j spi. el fin Parts
Poly R ¹ "1 ^C 3 ^H 7
^C 5 ^H 9
^C 2 ^H 5 ⁺ 8th 1 si ι! -sst / k 60
1 a're 20th
ίο ³
ίο ⁴
ίο ⁴ ίο ²
2 > io ⁷ i-io ³
2 > io ⁷ ^ 10
₃ o ³
ιο ^δ
: ο ^δ 4 · 7- 10
10 ³ y
ίο ⁴ ?
10 ⁴ I. 10 y
f9 i \ ^r r. olefin Λ O 1 C +) fierstellunci there 1
k
1
1 k 1
k
1
1 T * ^l0 \ 2 10 3-10 ²
2 9 * 10 1- 3 4 · 6 ·
2 ·
6 ·
7- s; > 1θ 'j PE ^C 12 ^H 25 ^C 3 ^H 7
^C 3 ^H 7 Ta ~ SSt ₁ * 1 5- 8-10 "
^{> 10} 7 8-20
4th S- 3-10 '
> io ⁷ 1-30 'ϊ
> ιο ⁷ ί
> ιο ⁷ _! 7- PE 0.5 ^C 38 ^H 35 ^C o ^H - - ) + k k
SSt
SSt * m
1
1
ra k
St.
SSt, * 6- 8th· 2-10
9
8 · 10
i-io ⁴ 1-
6-
! ·
O 5- 1* 5 · ο PT. 0.5 ^C G ^H 13
^C 12 ^{] I} 25
^C 1Ä ^K 23 ° 2 ö 1- t si k k 6-
1-
4 ·
9- O co
ο 7 ^J I2
FE 0.5
0.5
0.5
0, 5 . '. >' ο 1 ^C 3 ^H 7 (+) 1
k
1
1 k
St *
S StL * 7 · 4-10 ""
> io ⁷
> io ⁷ 3- 6 · 98 18/1 ^C 14 ^H 29 ⁺ k k k > 1 3.3Ο ³ FL '
ri: 0.5
0.5 I r- υ ^CH 3 - k
SSt
SSt. * SSt * SSt * 9- 3 P ^r 0, 7: 3 ÜO 2χ ^C 2 ^H 5 4th 4th k k k k 6 * · 'I ^C 12 ^H 23 + ⁺ k SSt * k 1 1
j PP 0.75 k k * PB ^C 14 ^H 29 ⁺ SSt * k PB 0.75 ^C 12 ^H 23 k ϊ l i PB 0.75 Comparative example k v) Cyclo- 12 y c) 3 3 ^V > j ³⁴ I. ι

Claims (2)

9 O.Z. 2585 10/20/71 claims 1. Antistatic molding compositions and moldings made from polyolefins with additions of nitrogenous compounds, characterized by the application of compounds of the formula R ₁ -NH-CH ₂ -CH ₂ -CH ₂ -Kh-CO-R, where R »denotes an alkyl, alkenyl or cycloalkyl group with up to 26 carbon atoms and R ₂ denotes an alkyl or alkenyl group with 1 to 5 carbon atoms, optionally together with up to equivalent amounts of organic or inorganic acids. 2. Antistatic molding compositions and moldings according to claim 1, characterized by a content of 0.01 to 2.5% by weight, based on the molding compounds, of connections of the claimed type. 309818/1111