DE2124874A1 - Use of tertiary amino esters as antistatic agents - Google Patents

Description

Case 150-3172

Use of tertiary amino esters as antistatic agents

It is known that moldings, fibers and films made from many plastics, such as polyolefins, polystyrene, polyamides _/ polyesters, polyacrylonitrile or polyvinyl chloride, have the property of being more or less electrostatically charged. Numerous methods have been proposed in order to prevent or at least reduce this electrostatic charge. It is known, for example, to change the surface of fiber bodies with the aid of antistatic agents in such a way that static charging is prevented. The protection achieved in this way, however, only lasts until the applied layer has been wiped off or loosened through the use of the objects. However, permanent effects can only be achieved if antistatic products are incorporated into the plastics, which slowly migrate to the surface and

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Develop an antistatic effect for a long time. For practical purposes, it is necessary that such an antistatic agent, when used in low amounts, has a sufficient effect and does not adversely affect the properties of the substrate. In particular, it should also have good heat stability and not accelerate the rate of decomposition of the substrate at high temperatures. It has now been found that thermoplastic compositions containing a tertiary amino ester of the formula

contain, - . -

in which R is an aliphatic, saturated or unsaturated, optionally substituted radical having 1 to 24 carbon atoms,

Rg.a hydroxyalkyl radical with 1 to 5 carbon atoms or a radical (CB ₀ O) -H,

Λ cLJi. Ul

R ^ is an alkyl radical with 1 to 5 carbon atoms ^ or R _?

η is a number from 1 to 4-

m is a number from 2 to 10 '

and χ is one of the numbers 2 or 2, has particularly advantageous antistatic properties

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award.

The amounts of tertiary amino esters to be used can vary within wide limits, e.g. from 0.01 to 5 percent by weight. Additions of 0.1 $ of the amino esters already give the above Formula based on the weight of the polymer very good antistatic effects. In the further the color and the transparency of the polymers and their mechanical properties are practically not reduced.

A surprising property of these antistatic agents is their extraordinary good thermal stability, as found in particular in the processing and heat aging of plastics shows and in contrast, for example, to the amines listed in the German Auslegeschriften 1.247.008 or 1.248.922, which only together with amine stabilizers provides sufficient heat stability on v / iron, even without any additives without impairing the appearance of the plastics under thermal stress can be used.

The radical R, -COO is derived, for example, from an alkanoic or alkene carboxylic acid with 2 to 25 carbon atoms such as acetic acid, propionic acid, butyric acid, iso-bitter acid, valeric acid, iso-valeric acid, Caproic acid, oenanthic acid, caprylic acid, pelargonic acid, Capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, acrylic acid, Methacrylic acid, crotonic acid, oleic acid, elaidic acid fer-

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ner of alkanoic or alkene carboxylic acids, the substituents such as Z, B. H3 ^r can carry hydroxy or alkoxy groups, such as glycolic acid, ■ lactic acid, 2-methoxy-, ^ -ethoxy-, 3-n-butoxy-> Jn-amyloxy, 2-n-octyloxy-, J5- (2'-ethylhexyloxy ) «^ -N-decyloxy-, J-cetyloxycder 5-olyloxypropionic acid, the corresponding 2-alkoxyacetic acids. 4-methoxy- or ethoxybutyric acid or ricinoleic acid. Doubly or triply unsaturated carboxylic acids, such as sorbic acid, linoic acid or linolenic acid, are hardly considered because of their sensitivity to oxygen (drying properties). . '

The radical R ₂ is, for example, a 2-hydroxyethyl, 2- or 2-hydroxypropyl 2-, 3- or 4-hydroxybutyl or 5-hydroxylpentyl radical or a polyoxyethylene or polyoxypropylene radical with 2 to 10 oxyalkylene units.

The radical R ,, when it stands for an alkyl radical is, for example, methyl, Ethyl, n- or iso-propyl, n-, iso-, sec. or tert. Butyl, η- or iso-amyl, 2- or 3-amyl, tert. Amyl.

Preferred compounds of formula (i) are those in which R ^

an optionally substituted alkyl radical with

7 to 17 carbon atoms (in particular with 11 or 17 carbon atoms) or an alkyl radical of a mixture of fatty acids containing 8 to 10 carbon atoms (or R ₁ -COO- is from valeric to stearic acid, oleic acid or ricinoleic acid or from an alkoxy acetic acid or -propionic acid with about 4 to 15 carbons-

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derives substance atoms in the alkoxy radical). R is a hydroxyalkyl radical with 2 carbon atoms

R-, an alkyl radical with 1 to 4 carbon atoms or Rg and η = 2.

The novel useful compounds can be prepared by known processes, for example, -or by heating equimolar amounts of triethanolamine and carboxylic acids such as fatty acids fatty acid mixtures währer .-. D several hours to temperatures of from 1 ^ 0-190 ⁰ C with elimination of water. Instead of the free carboxylic acids or mixtures thereof, it is also possible to use their esters, anhydrides or else carboxylic acid halides. From this manufacturing process it also follows that the

- Effective compounds are not always obtained as chemical individuals, but often occur as mixtures. The antistatic additives can be used in thermoplastics such as polyamides, polystyrene or, in particular, polyolefins such as them obtained by high and low pressure polymerization of ethylene, propylene, butene- (l) or pentene- (l), by mixing be incorporated in the heat and under pressure. A good mixing of the thermoplastics with the antistatic agent can can be achieved e.g. with a mechanical mixing device or the antistatic agent can be mixed in a suitable organic

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Dissolve, disperse, suspend or emulsify niche solvents and the solution, dispersion, suspension or emulsion Add polymer powder to aem and stir thoroughly. The solvent can be removed e.g. by distillation. One can also incorporate the antistatic agent into the polymer Carry out directly on the roller or e.g. during injection molding in an extruder. The antistatic masses can be further processed, for example, by pressing, injection molding, spinning or calendering. You can also common additives such as plasticizers, dyes, pigments, Contain lubricants or fillers.

The assessment of the antistatic behavior of the inventive Molding compounds is carried out by measuring the surface resistance at 65 ^ rel. Humidity and 22 ° C according to DIN

The testing of the Hitzestäbilität equipped with the anti-static agents thermoplastics is made by laying of the specimens in a forced-air oven at 100-13O ⁰ C under visual assessment of discoloration after certain heat exposure time.

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In the following examples, which illustrate the invention without however, to limit them, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

example 1

400 parts of polyethylene (Lupolen 24j5O H, melt index 1.2-1.7), produced according to the letterpress process, are made with 0.4 parts Triathanolamine monolaurate mixed homogeneously for 20 minutes and the mixture is then processed into 1 mm thick plates on the injection molding machine. After 48 hours of storage at 22 ° and 65 # relative humidity, the surface resistance is determined. On another sample, the heat stability is achieved at 100 ° checked. The results are compiled in the table below. . ·.

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Example 2

200 parts of polypropylene (Carlona PM 6l melt index 5 * 0) mixed homogeneously with 1.0 part of triethanolamine monostearate and pressed the mixture on the rolling mill to give sheets 1 mm thick. The surface resistance is measured as in the introduction described, the heat test is carried out at 1 ^ 0 °. The results are compiled in the table below.

Example 3 *

500 parts of polyethylene (melt index 1.2-1.7), produced by the high-pressure process, are _{mixed homogeneously with 0.5 parts of coconut fatty acid {Co-C, 0} ) ~ triethanolamine monoester for 20 minutes and the mixture on the injection molding machine to form plates of Processed lmm thick. The surface resistance and heat stability are measured as described in Example 1.

The results are compiled in the table below.

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example

300 parts of polypropylene are mixed with 1.5 parts of methyl diethanolamine monolaurate mixed homogeneously and the mixture "pressed on the injection molding machine to form sheets of lram thickness. The resulting Samples show no discoloration and have a very low surface resistance, as shown in the table below can be seen.

Example 5

Similar results as in Example 4 are obtained if to ^ 00 parts of polypropylene 1.5 parts of butyl diethanolamine monolaurate can be used.

Example 6

4-00 parts of polyamide-6 are mixed with 2.0 parts of triethanolamine monolaurate intimately mixed and the mixture pressed on the injection molding machine to form sheets 1 mm thick.

The surface resistance is measured as in the introduction described. It amounts to one with the antistatic

Q 11

equipped plate 10 ^ ohms compared to 10 ohms for a plate Made of polyamide that does not contain any antistatic agents.

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example Polymers Ver
binding Antistatic Be
drawing additive
in % Surfaces-
resistance
(0hm) Assessment of the ver
yellowing Polyethylene
(without addition) Mt 10 ¹² after 16 hours
100 °: very easy
yellowish 1 . Polyethylene Triethenolamine: · '
monolaurate 0.1 10 ⁸ after 16 hours
100 °; very easy
yellowish Polypropylene
(without addition)' - - 10 ¹ ' after 16 hours
1 ^ 0 ° ϊ very easy;: ·,
yellowish ■ '■' 2 Polypropylene . Triethanolamine
monostearate 0.5 1O ⁹ '5 after 16 hours at 13
130 °: no Vergil
exercise Polyethylene Coconut acid
(Co-C ₁₀ ) -triätha-
nolamlnester 0.1 . ίο ⁸ after 16 hours
IJO ⁰ ; no Virgil
exercise 4th Polypropylene Methyl diethanol
amine monolaurate 0.5 10 ⁸ '3

Claims (9)

Claims 1. Use of tertiary amino esters of the formula B ₁ -COO-C _n H _2n -N / ² (I) ^H 3 wherein R is an aliphatic saturated or unsaturated optionally substituted radical with 1 to 2k carbon atoms,
Rp is a hydroxyalkyl radical with 1 to 5 carbon atoms or a radical (CLH ₀ -O) -H, R ^ is an alkyl radical with 1 to 5 carbon atoms or Rp, η is a number from 1 to 4
m is a number from 2 to 10 and χ mean one of the numbers 2 or 5, as antistatic agents for polymeric substances, especially polyolefins. 2. Use of tertiary amino esters of the formula ^ CHpCH OH R ₁ - COOC ₂ H ₄ N ^ R ₂ wherein R _{1 is} an alkyl radical having 7 to 17 carbon atoms and 109853/1650 Rp is an alkyl radical with 1 to 4 carbon atoms or CH ₂ CH ₂ OH, as antistatic agents for polymeric substances. 3 · Use of tertiary amino esters according to claim 2, characterized characterized in that R- is an alkyl radical with 11 carbon atoms means. P. 4. Use of tertiary amino esters according to claim 2, characterized characterized in that R is an alkyl radical with 17 carbon atoms means. 5. Use of tertiary amino esters according to claim 2, characterized in that R ₁ denotes an alkyl radical of a mixture of fatty acids which contain 8 to 10 carbon atoms. 6. Use of the tertiary amino ester of the formula ^ .CH ₂ CH ₂ OH ^ CH ₂ CH ₂ OH as an antistatic agent for polymeric substances, especially polyolefins. 7 · Use of the tertiary amino ester of the formula CH-CH OH C, "H ^ COOC" H "N '* * 109853/1650 as an antistatic agent for polymeric substances, especially polyolefins 8. Use of the tertiary amino esters of the formula ^ CH ₉ CH ₀ OH C ₇ -C _Q alkyl-COOC _p H, N ^ ^{d 1 y} ^ CH CH OH as antistatic agents for polymeric substances, especially polyolefins. 9. Polymeric substances, especially polyolefins, with the tertiary Amino esters of the formula I have been given an antistatic finish. The patent attorney 1 109853/1650