DE2152950A1 - ANTI-ELECTROSTATIC MOLDS AND MOLDED BODIES MADE OF POLYOLEFINES - Google Patents

Description

Ant! Electrostatic porm mass e ns and moldings made of polyol efinen 2. Addition from DBP (patent no. P19 54 291.7)

The invention relates to a further embodiment of the antistatic molding compositions and moldings made from polyolefins with additions of nitrogen-containing compounds of the formula

Ro - 0

CH.

CH

according to patent application P 19 54 291.7

As is well known, plastic parts made from polyolefins tend to become exposed to electrostatic charges during storage and use to a large extent to attract dust, which considerably reduces their utility value.

Various means have been suggested to get around this Avoid difficulties. So you can coat the surfaces of 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. More lasting effect achieved if you work the anti-static additive into the polymer material and make molded parts from these mixtures

54/71

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BATH ORIGINAL

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10/21/1971

represents. These additives include, for example, quaternary ammonium salts, Polyalkylene glycols and polyalkylene glycol esters. If even better Properties, for example, have the already proposed oxethylates of alkanols and alkylaryl phenols (BE-PS 536 623, GB-PS 731 728), but these compounds tend to exude if you use the amount necessary for sufficient effectiveness incorporated into the plastic.

fe A further increase in the anti-static effectiveness can be achieved with nitrogen-containing compounds, such as amides and arrainocarboxylic acid derivatives (FR-PS 1 377 803-8), oxazolines and to an even greater extent with alkylaraines (BE-PS 655 182 and 655 183), in particular with oxethylates of alkylamines (BE-PS 645 800, FR-PS 1 345 827 and 1 322 626, DT-AS 1 228 056), in which the bis-hydroxyäthylderivate the are most effective. However, these compounds often have the property that in the first few days after production of the molded part the formation of a surface film is still too small, so that the additive does not immediately become fully effective. But this has As a result of the processing, e.g. mold separation during injection molding, generally very high electrostatic The charge cannot flow off immediately, so that within a few days the moldings become unsightly due to the attraction of dust even more so than the dust supply in manufacturing facilities due to the difficult to avoid dust swirling is generally very large.

In the patent literature, alkylimidazolines and tetrahydropyrimidines are used described as highly effective, of which the latter are particularly effective on the surface of fragments of form. However, this very often leads to the formation of undesirable deposits.

309817/11 * 8

BATHROOM LOCAL GINAL

2152350

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10/21/1971

The task was therefore to make polyolefins antistatic equip and use the gate parts of the amines and cyclic Aininaniiäe without the above-described after To have to accept parts of the late effectiveness and the formation of deposits.

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

R - 0 CH ₂

- CH ₂

where χ = 2 to 6, y and ζ = 2 or 3, π and η = 0 to 5 and R. a branched or unbranched alkyl or alkeny group with 5 to 25 carbon atoms, optionally as quaternary Salts or together with up to equivalent amounts of organic or inorganic acids.

In this formula, χ are preferably 2 and 3, y and ζ are preferred 2, m and η preferably 0 and 1 and E is one of the "hydrocarbon radicals" mentioned with preferably 9 to 1?, in particular 11 to 13 Carbon atoms.

On the one hand, using the compounds is their application onto the surfaces of the moldings (e.g. by dipping or To understand spraying of the mixtures, if desired dissolved in water or organic solvents), on the other hand the incorporation of 0.01 to 2.0 wt .- '^, based on the molding compounds, the tetrahydropyriiaidino.

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BATH ORIGINAL

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10/21/1971

Ala moldings and molding compounds are mainly injection molding , Extrusions and deep-drawn bodies as well as eolias, threads and fibers eu understand.

Suitable anti-static equipments with additives Polyolefins are, for example, high and low pressure polymers made from ethylene, propylene, butene (1), pentene (1) etc., in particular all types of polyethylene with molecular weights between 20 and 150,000, polypropylenes with molecular weights between 100,000 and 800,000, polybutenes- (1) with molecular weights ™ Bwiechen 300,000 and 3,000,000, polypentene (1) and mixed polymers and polymer blends thereof.

Polyolefins such as those obtained by means of feather printing processes are preferred According to Ziegler and Natta, in particular, it is obtained, especially with the use of mixed catalysts made from titanium compounds such as fitan tri and tetrachloride or halogenated titanic acid alkyl esters on the one hand and organoaluminum compounds such as aluminum trialkyls, alkyl aluminum halides and / - «eesquiohloriden on the other hand.

All group R can be used and, for example, the n-heptyl, P n-octyl, triaethylpentyl, n-nonyl, n-undecyl, n-undecenyl, i-tridecyl-, n-tetradecyl-, n-pentadecyl-, n-heptadecenyl- and n-heptadecylreet. Preference is given to the n-undecenyl, n-Undecyl ~, n-Dodecyl, n-Tridecyl, i-Tridecyl radical or mixtures out of this.

Suitable compounds are e.g. 1- (Aniinopropyl) -2-eicosyltetrahydropyrimidine, 1- (Bis-hydroxyäthyloxyäthyl-aininoäthyl) ~ 2-heptyltetrahydropyrimidine, 1- (Hydroxyäthylaminoäthyl) -2-heptadecenyl-tetrahydropyrimidine, 1 ~ Aminohexyl-2-undecyl-tetrahydro-pyrimidine.

309817/111 β

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10/21/1971

Particularly suitable compounds are e.g. 1- (bis-hydroxyethylaminoethyl) -2-undecyl-tetrahydropyrimidine, 1- (aminoethyl) -2-triacyl-tetrahydropyrimidine, 1- (hydroxyaminoethyl) -2-undecyl-tetrahydropyrimidine.

These compounds are obtained in a known manner by reacting aminoalkylaminopropylaraines with carboxylic acids or theirs Derivatives such as esters or nitriles. The free carboxylic acid is advantageously used and the resulting carboxylic acid is removed Water (2 moles per MbI tetrahydropyrimidine) azeotropically the reaction mixture, with xylene being used as entrainer.

In addition, a number of other manufacturing processes are known, however, they are generally of no practical importance.

The oxyalkylation - according to the choice of y and z, oxyethylation or oxypropylation - leads to the addition of moles of the alkylene oxide without catalysts, so the bis-hydroxyethyl derivative is formed when ethylene oxide is used, for example. In the presence of catalytic amounts of alkali, for example in the form of sodium hydroxide, the aminoalkyl tetrahydropyrimidines take up 1 to about 500 units of alkylene oxide. But if you go for the catalytic conversion of the obtained without the use of Katalyeatoren bis-hydroxyalkylderivaten'aus, we obtain oxyalkylates narrower molecular weight distribution, staying with alkylene · implement equal the free amine in the presence of alkali The closer to the molecular weight distribution on the sets the desired degree of oxyalkylation, but the more effective the additive. For this reason, the last-mentioned method of preparation is preferred if one does not

309817/1118

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ZTTTuTWT

the mono- and di-hydroxyalky! derivatives used at all. From this manufacturing process it also follows that the claimed active compounds are not all chemical Individuals are obtained, but often as a homologous mixture in terms of the number of oxyalkylene groups. As a rule, this does not play a role, especially when the molecular weight distribution is within narrow limits. It Such is also possible, as the formula given above shows Establish and successfully use connections in which y and ζ are different from one another. One wins such Compounds by, for example, replacing only one hydrogen atom of the amino group with a hydroxyalkyl group replaced or if the compound obtained in this way is reacted with another oxyalkylating agent, for example the tf-hydroxyethyl-N-hydroxyaminopropylamine derivative is obtained. In the case of the higher oxyalkylated compounds, Oxyäthylnnd Be oxypropyl groups in a chain. Finally, one can also substitute similarly or dissimilarly Connections or homolog cuts therefrom with one or more other connections satisfying the formula mixed use.

The tetrahydropyrimidines can also be used as quaternary salts, e.g. as reaction products with chloroacetic acid or its alkali salts or chlorohydrin or alkyl halide, or as salts Bjit acids, e.g. with mono- and dicarboxylic acids (such as acetic acid, lauric acid, oleic acid, oxalic acid, tartaric acid, succinic acid or DoÖecanedioic acid (1.12)) and / or with hydroxycarboxylic acids (such as Lactic acid, glycolic acid or ricinoleic acid) and / or phosphoric acid or their alkyl partial esters or with sulfonic acids (such as alkanoic or alkylbenzenesulfonic acids) are used, whereby the base character of the compounds is reduced or abolished *

303817/1113

- 7 - O.Z, Γ.588

STTiO. 1971

The salts can be prepared, for example, by Mixture of equimolar amounts of one or more tetrahydropyrimidines and one or more acids, optionally in the heat, converted into a homogeneous melt by intensive stirring and then allowed to cool or that both components and the combined solutions are taken up in suitable solvents evaporates to dryness, which largely eliminates the risk of possible discoloration. You can introduce new additives into the polyolefin in various ways. For example, you can use the polyolefin with the anti-static Immediately transform the agent into a homogeneous mass in a mixer. In general, everyone is commercially available for this purpose Suitable for high-speed mixers. You can also first give the polyolefin a higher than the desired percentage Mix in the antielektrostatißchen agent and this mixture then bring to the desired antistatic content by mixing in more polyolefin. One can also dissolve, disperse, suspend the antistatic agent 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 also all others easily Distillable solvents are suitable for this purpose. But you can also incorporate the antistatic agent into the polyolefin directly on the roller or e.g. during injection molding in an extruder.

The anti-electrostatic behavior of the moldings is determined by the dust test method, through information about the dustiness, de » ¹ the test specimens a) in a normal atmosphere (exercise), b) when sprayed with a mixture only, flight -

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BATH ORIGINAL

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10/21/1971

Ash and soot (dust test) and c) when sprinkling with a Special powder (color powder test) subject to, checked. These tests are carried out on test trays (42 × 250 × 320 mm).

If

Another test, carried out on spray plates (4 x 65 x 120 mn), consists in measuring the electrical surface resistance according to DIN 53482. The ash dust test is carried out in the following Carried out this way: 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: +, it relates So calibrate the effect of the incorporated substance). Furthermore, 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 dusting takes place the division - also semi-quantitative - into none (k), very light (el), light (1), medium (n), strong (st) and very strong (sst) dustiness, observed 8 days after manufacture. Liohtenberg figures are marked with *.

The so-called dust test is that the samples are sprayed 1 day after preparation in a chamber of a Feststoffdüee with a mixture of 75 i "fly ash and 25 ί * carbon black. The classification is the same as for normal deadening.

The so-called colored powder test, carried out 1 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 are attracted to different places on the plastic surface (red

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te places = areas of positive charge, blue areas = areas of negative charge on the plastic surface).

Based on 34 examples and comparative examples, the table shows that the alkylene group in the side chain preferably contains 2 and 3, and if possible not more than 6 carbon atoms should (Example 21) that the ethylene oxide derivatives, the propylene oxide derivatives still surpass (Examples 9 to 11) that the number of oxalkylene groups is preferably a total of O to 2 (x + y) should be (Examples 3, 9, 25, 27 versus 8, 12, 13, 28) and that the number of carbon atoms in the alkyl group R is preferred should be around 11 (Examples 2 to 7).

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, an average molecular weight of 470,000 and the reduced viscosity of 4 and PB a polybutene (1) with a density of 0.910, an average molecular weight of 2,000,000 and a reduced viscosity of 4.

309817/1118

-40-

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309817/1118

Continuation table

O.Z. 2588

Poly Parts R-C I.
Λ TJ -CH, ² ^ CH ₀ y ^ H 2y η Ash test 8th - normal dust Color powder 8th 1
k
St * 1
St.
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k
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7-1Ο ³
> io ⁷ 8-10 ⁴
6-1Ο ⁴
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1 · 10 ⁴
> io ⁷ •At- ole to 100 L · H
X ? Cl to to Z 0
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2 I. si si si at 23 ° α β ιο ⁴
l-io ⁴
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k
St. k
k
si k
k
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3-3Ο ³
6-10 ³ 6-10 ³
8-10 ³
4-3Ο ⁴ 9.1O ²
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2 2 0
1
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m k.
m k
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2 2
2 0
5 (+) - k 1 1 1 2-1Ο ³
3.1O ³
2Ί0 ⁴ 3-OK ⁴ l-io ⁵ 5 ⁴ PE
PE
PE 0.5
0.5
0.5 ^C 13 ^H 27
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4th
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4-10
5-1Ο ⁴ ; 27
28 PP 0.75 ^C 17 ^H 3p
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fs? co cn

- 12 - OZ 2 586

October 21, 1971 "

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 having a density of 0.930, an average molecular weight of 1,000,000 and a reduced Has a viscosity of 1.18, comparable results are obtained. The same applies when using a polypropylene with a density of 0.905, the average molecular weight of 340,000 and the reduced viscosity of 3 or with the density of 0.905, the average molecular weight of 600,000 and the reduced viscosity of 5 and when using a polybutene (1) with a density of 0.910, the average Molecular weight of 1,300,000 and the reduced viscosity of 3 or with a density of 0.915s the average molecular weight of 800 000 and the reduced viscosity of 2.-

309817/1118

Claims (2)

- 13 - O.Z. 2588 10/21/1971 "Claims 1. Further training of the anti-static molding compounds and molded articles made of polyolefins with additions of nitrogen-containing compounds of the formula R ₂ -C according to patent application P 19 54 291.7,
marked by the application of compounds of the formula JI - CH ₂ - where χ = 2 to 6, y and ζ = 2 or 3, m and η = 0 to 5 and R is a branched or unbranched alkyl group with 5 to 25 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, characterized by a content of 0.01 to 2.0 percent by weight, based on the Molding compounds, of compounds of the claimed type. 309817/1118 INSPECTED