DE1694122A1 - Antistatic treatment of macromolecular substances I - Google Patents

Description

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FARBWERKE HOECHST AG.

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Frankfurt (M) -Hoechst

Appendix I.

to the patent application Fw

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• Gi / kr 5101

Antistatic treatment of macromolecular substances I

High polymer organic compounds are generally good insulators and prone to electrostatic charges. These charges can occur under unfavorable conditions become so strong that a spark discharge can occur. Most of the time, however, the electrostatic charge builds up annoyingly noticeable in that the high polymer Connection produced molded parts too strong. Tend to draw dust and protective parts, whereby z. B. the well-known crow's feet. arise and the objects, such as z. B. films, fibers and fabrics, dirty quickly.

The electrostatic charge represents the use of high polymer Substances for many fields of application in question. There are hence various methods of reducing the electrostatic Chargeability has been studied, Sq can through subsequent impregnation of the surfaces of the moldings with. Compounds suitable for use as antistatic agents are electrostatic Chargeability and the surface resistance

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be reduced. However, the antistatic effect is not permanent and is greatly impaired by the possibility of wiping off the applied antistatic agents, _f

Those suitable as antistatic agents. yes substances should, In order to be technically usable, they have the following properties in addition to an antistatic effect: Resistance, i.e. No discoloration at processing temperatures up to 300 ° C, a very low odor, cannot be washed out with water, no exudation from the high polymer compounds and a certain ability to migrate in the High polymer to be able to get to the surface of prefabricated parts} but the ability to migrate is allowed again not be too big so that the antistatic additive Resists rubbing or wiping. Furthermore, the antistatic effect should be present immediately after processing and not caused by additional flame treatment or high-frequency discharge have to. *) can be incorporated

It is more advantageous to use the additive that acts as an antistatic agent to be incorporated into the high-polymer compound, resulting in a durable and economical antistatic finish will. Various ionic and non-ionic substances are already known as suitable antistatic agents, the former, i.e. salts, being different because of the risk of corrosion have not proven themselves during processing. On non-ionic Phosphoric acid derivatives, special amines and amides such as fatty amines and fatty acid amides or alkylene oxylated are already additives Amines and amides, also polyalkylene glycols, amino alcohols and their esters as well as conversion products of fatty acids or higher alcohols with low molecular weight alkylene oxides known. !

) The previously known antistatic agents meet some of the requirements to be met by an effective antistatic agent. * This is how the antistatic properties of polyolefins

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by the addition of N-hydroxyalkylalkanolamines, as in the method according to the Belgian patent specification 654 049 described, although neatly improved, but show that Disadvantage that the compounds migrate very easily. This makes the plastic surfaces difficult to print. At the same time the permanence of the antistatic effect disappears e.g. B, in drawing fibers and Foils. Furthermore, when processing, e.g. B. after the injection molding process, depending on the temperature one more or less discoloration of the polyolefin noticeable. In spite of a useful antistatic effect, such side effects only require very limited possible uses.

It has now been found that macromolecular substances can advantageously be given an antistatic finish by using o.o5 to 4 .Gew. %, Preferably 0.3 to 1.5 wt.%, Based on the high polymer compound at reaction products of primary and / or secondary amines of the general formula R ₁ R ₂ NH, wherein R ₁ is an aliphatic hydrocarbon radical having 4 to 22 carbon atoms, preferably 12 to 18 carbon atoms and R _{2 represent} a hydrogen atom or an aliphatic radical with 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, with oxiranes of the general formula

where R, a hydrogen atom or an alkyl radical, bits 1 to C atoms and R ^ denotes a hydrogen atom or a methyl group.

It was particularly surprising that the aromatically sub-8tltulez * th oxiranes in the reaction with the known above amines provide very good antistatic agents, which at the same time still in an excellent manner with both aliphatic and Compatible with polymers composed of aromatic monomers and of very high permanent antistatic effectiveness are. '1-098-29 / 1 398

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As oxiranes according to the invention come ζ. Β. Phenylene oxide (Styrene oxide), p-methylphenylethylene oxide, oUMethyl-diphenyl-ethylene oxide («λ-methylstyrene oxide) or p-dodecylphenyl-ethyl-oxide, phenylethylene oxide and p-methylphenylethylene oxide are preferred.

Suitable amines are e.g. butylamine, octylamine, decylamine, Laurylamine, stearylamine, eicosylamine, dibutylamine, N-methyloctylamine, N-methyldodecylamine, N-ethyldodecylamine, N-methyl stearylamine, N-ethylstearylamine or mixtures thereof and amines from talc fatty acids, coconut fatty acids and the same. .

Reaction products of phenylethylene oxide or p-methylphenylethylene oxide have proven to be particularly advantageous primary and secondary amines, preferably fatty amines, proved.

The implementation of the above-mentioned oxiranes with the primary or secondary amines takes place in the simplest case Normal pressure in 1 to 4 hours by stirring the two components together at temperatures between 12o and 24o ° C, preferably between 14o ° and 18o ° C, with the reaction temperatures for the secondary amines from.Hteri see reasons higher than the primary. The molar ratio Oxirane to amine is when using primary amines 2: up to 1: 1, preferably 1: 1, when using secondary amines 1: 1.

The manufacturing process of the antistatic agents according to the invention is particularly advantageous because the output compounds are stoichiometric can be used, react quickly and quantitatively and therefore the removal of an unreacted Component or post-purification of the reaction product is not necessary.

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The addition of the antistatic agents according to the invention improves also the sliding behavior of the highly polished connections very significantly during processing and reduces that unwanted blocking. The antistatic agents according to the invention mainly increase the electrostatic chargeability considerably reduced, as a result of which the surfaces of the finished parts no longer attract dust. Already at When using small amounts, the antistatic agents according to the invention show a very good: * e permanent effectiveness,

'". They can also take it

high temperatures during processing without discoloring or migrating, show no reactions with other additives such as stabilizers or pigments and do not corrode during processing and use. There is also good compatibility with a variety of high polymer compounds. An etiose sweat could not be observed.

According to the invention, a large number of macromolecular substances can be given an antistatic finish, preferably Polyolefins and polyesters. Polyolefins are homopolymers of ethylene, propylene, butene-1, ^ -methylpentene-1, and styrene, also copolymers of ethylene and propylene and / or butene-1 and copolymers of 4-methylpentene-1 and 1-olefins, also copolymers of styrene and acrylonitrile, Methyl acrylate and / or diolefins such as butadlene-oil, 3 Polyesters are e.g. B. polymeric esters of terephthalic acid and glycols with 2-lo carbon atoms. Aueii paint » raw materials such as polyvinyl acetate, alkyd and unsaturated; ® polyester resins can be determined by the sentences according to the invention Equip antistatic.

Adding the antistatic to the high polymer compound can be in the course of the manufacturing process or by subsequent Incorporate z. B. by Trookeineinatlsehen, rolling in, Addition when granulating or in a commercial one

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Banbury Miecher done. The antistatic can be used as a solution in a solvent swelling the high polymer compound such as jz, ft, chlorinated hydrocarbons or non-swelling 'like z. B. low molecular weight aliphatic alcohols and ketones / e or added as a suspension or dispersion be, with the liquid phase after treatment the powder or granulate is evaporated. *) Solvents

Otherwise usual additives to high polymer organic compounds such as stabilizers, fillers, dyes, lubricants, plasticizers or pigments affect the antistatic Effectiveness of the antistatic agents according to the invention not; also be the mechanical and thermal properties as well the heat and aging stability of the high-polymer compounds are not impaired by the antistatic agents according to the invention. Depending on the requirements, it can be advantageous to use one or more of the antistatic agents described to be used together or together "with known antistatic agents.

The antistatic compositions according to the invention can be used, as is customary, in compression, injection molding, extrusion or deep-drawing processes are processed. The varnish resins to which the antistatic agents have been added can also be used in the usual way as varnishes.

Examples;

Percentages given in the examples are percentages by weight. The antistatic agents specified in Examples 1 to 14 were mixed with pulverulent plastic in a high-speed mixer in an amount of 1% by weight , based on the polymers. Liquid or highly viscous antistatic agents were used as solutions in equal amounts, the solvent being quantitatively evaporated off after mixing with the plastic powder at temperatures of 50 ° to 100 ° C. in a vacuum at 100 mm Hg.

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From the resulting mixtures with polystyrene and polyethylene terephthalate were placed between chrome-plated Meeeingplatten 1 mm thick press plates produced at a pressure of 100 ISp / em The processing temperature for polyethylene terephthalate was 27o ° C, for polystyrene 15o ° C.

Powdery mixtures with polyethylene or polypropylene were extruded into a strand by means of an extruder,. which was chopped into small pieces by a granulator. These granules were mixed with the aid of an injection molding machine at temperatures between
Test plates processed.

1 mm thick at temperatures between 22o ° C and 29o ° C

To test the antistatic effectiveness, frictional electrical voltages generated on test plates were compared with one another compared. For this purpose, a cloth covered with a woolen cloth rotating at constant speed (2j5o rpm) Cylinder on a sample that can be moved horizontally back and forth

(7 cm 7 cm χ 1 mm) generated static charges. The maximum electrostatic charge (volts) due to repeated friction processes was determined by a probe which was fixed 5 cm away from the test plate and is given in the table as V ₁ . V ^ is the value of the electrostatic charging of a specimen on which wet wiped 5 hours at room temperature and dried _cliiann: was measured.

To test the antistatic effectiveness of the substances according to the invention, the following soot test was also carried out: The test plate (7 cm × 7 cm × 1 mm) was moved back and forth ten times over a distance of 30 cm under slight pressure on a standard cloth (wool) and placed in the o , 5 cm distance over a layer of soot. In the following table: (+) black attraction and (-) no black attraction. All measurements were carried out at 20 ° C and 50 % relative humidity (standard atmospheric conditions)

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In the examples in the table, the antistatic agents were used in a concentration of 1% by weight , based on the high polymers. The values show the favorable electrostatic behavior of the high-polymer compounds equipped with the antistatic agents according to the invention.

After 8 days of storage of the test specimens at temperatures of 100 ° to 12o ° C and cooling to -4o ° C no exudation of the antistatic agents according to the invention was observed.

Unless otherwise specified in the table, oxiranes were used and amines reacted in a molar ratio of 1: 1.

ExamplePoly- added antistatic agent Oberf1 «Oberfl. soot

No. Meres spnng. voltage test V ₁ (Y) V ₂ (VJtS)

1 PE b) without > yjoo > J? Oo = + ·

la * "PE conversion product from -looo -15oo + _s

Stearylamine & Ethylene Oxide (ls3)

2 PE conversion product from -111 +52

Phenylene oxide +
Stearylamine.

3 PE conversion product from -259

Phenylene oxide +
Stearylamine (in a molar ratio of 2: 1).

4th PE Urea product
Phenylene oxide
Methylstearylamine the end
+ N- -3ÖO -21o + 5 PP c) without •> 37oo > 37oo - + 5a « PP Implementation product the end -lloo -13oo

Stearylamine and ethylene oxide (1: 3)

6 PP conversion product from -33ο -285

Phenylene oxide +
Laurylamine

7 PP conversion product from -215 -37 ©

Phenylene oxide +
Octylamine

8 PP conversion product from p- -4lo -175

Nonylphenylethylene oxide + N-dibutylamine

9 PS d), without -27oo -255o 4 *

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Example poly- added antistatic agent surface surface soot-

No. meres voltage · voltage »test

Vtxt \ ττ frfa} • t \ Y / ig V '^ /

PS reaction product from Phe- -74 -326

nylethylene oxide + stearylamine

PS Implementation product from Phe- -275 -47o

nylethylene oxide + N-methylstearylamine

PS reaction product of p- -114 -28o

Methylphenylethylene oxide + laurylamine

PETP e) without -21oo +

PETP conversion product from ^ -Me- -39o

ethyl-'i-phenyl-ethylene oxide +

Laurylamine.

a) = - wiped off with a damp cloth d) «PS - polystyrene

b) = PE - low-pressure polyethylene «) = PETP - polyethylene-

c) = PP - polypropylene rephthalate

3K = comparative examples with a known antistatic agent

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Claims (1)

Claim Use of conversion products of primary and / or secondary amines of the general formula R ₁ RpNH, where R is an aliphatic hydrocarbon radical with 4 to 22 C atoms and R _{2 is} a hydrogen atom or an aliphatic radical with 1 to 12 C Atoms, represent, with oxiranes of the general formula ι ⁴ ~ VC - CH ₀ \ / ² 0 ~ wherein Rr a Wasserst off atom or an alkyl radical having 1 to 12 carbon atoms and Rh, a Waaserstoffatom or a methyl group in an amount of o.o5 to 4 wt.% as antistatic agents for macromolecular substances. ♦
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