DE1811076A1 - Antistatic agents and polymer preparations containing them - Google Patents

Description

Awtis-ta'träi-tische agents and polymerizate- 'containing them PREVIOUS

The invention relates to antistatic agents for polymeric materials as well as polymer preparations containing these agents.

It is known that the electrostatic charging ability of polyolefins is reduced if a polyolefin is incorporated 0.01 to 5 wt .- ^ ₃ , based on the weight of the polyolefin, of a hydroxypolyalkoxyamide as an antistatic agent, for example

1) an N- (hydroxyalkylated) fatty acid amide, • 2) an alkylene oxide condensate of a fatty acid amide,

3) an alkylene oxide condensate of an N- (hydroxyalkyl! Erten) -Pett-

aäureamids or
.4) a mixture of two or more compounds of the

Groups 1) to 5),

■ v / o when the fatty acid amide contains 6 to 22 carbon atoms.

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It is also known that polyethylene has a tendency to accumulate electrostatic charges by incorporating a Ethanolamide to reduce lauric acid.

It is also known that an alkyl sulfonate with an alkyl ketene length of 4 to 30 carbon atoms, an alkylbenzenesulfonate with an alkyl chain length of 4 to 30 carbon atoms, a sulfonate of a polynuclear or condensed aromatic ring system with 1 to 2 alkyl groups with a chain length of 1 to 4 carbon atoms or a mixture of these sulfonates can act as an antistatic agent for styrene polymers.

It has been found that the use of the above-mentioned antistatic agents has certain disadvantages. For example, antistatic agents such as laurine diethanolamide, in sufficient quantities to achieve the desired antistatic properties, result in a significant reduction in the softening point of the polystyrene. This lowering of the softening point requires a longer expenditure of time for the production of injection molded parts because of the longer cooling time that becomes necessary in the injection molding cycle. Furthermore, ale's heat resistance of the moldings is also reduced. When using an antistatic agent, such as sodium dodecylbenzene sulfonate, the desired antistatic properties are achieved, but discolored compacts often result.

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The type of anti-static additives mentioned is customary less effective than a throwaway, i.e. the river of the ochmelzmaterials during the deformation becomes less favorable influenced than with an addition of e.g. lauric diethanolamide.

The object of the invention is therefore to create antistatic Agents which do not have the disadvantages associated with the above-mentioned antistatic agents.

A particular Au "were of the invention is to provide anti-static agents, lead kluszeiten to an excellent balance between the conflicting demands for short Spritzgußz ^ _f light flux of the compositions during molding and high ^v / ärmebe permanence of the moldings.

According to this, an antistatic agent is used for polymer material materials which, in terms of weight, contains a large proportion of an alkyl, aryl or alkaryl sulfonate and a coagulated proportion of an alkylalkanolamide or hydroxypolyalkoxyamide. The expression "large proportion ¹¹ =" means more than 50 ^c A ⁿ and "small proportion" - "50 f5 or less". The invention also includes polymers containing these antistatic agents. Preferred alkyl, aryl or alkaryl sulfo »ates include:

> '© "! Alkyl sulfonates with an alkyl chain length of 6 to 22 Carbon atoms,

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(b) Alkylbenzenesulfonates with an alkyl chain length of 6 to 22 carbon atoms,

(c) alkyl naphthalenesulfonates "with one or two alkyl groups,
which each have a chain length of 1 to 4 carbon atoms and

(d) the sulfonate of a dinaphthylmethane with one or two Alkyl groups, each of which has a chain length of 1 to 4 Have carbon atoms.

The antistatic agent contains an alkanolamide or a hydroxy polyalkoxy amide of an organic acid, which can be aliphatic or aromatic. A ne aliphatic acid having 6 to carbon atoms, such as lauric acid, is preferred. as
Alkanolamide, mono · «· or malkanolamide, usually mono or diethanolamide, can be used. Lauric diethanolamide is preferred as the alkanolamide.

The antistatic agent often consists of a solution or dispersion of the sulfonate in the alkanolamide. However, the ingredients can can also be added separately to the polymer on which they are to act, i.e. the antistatic agent can be added in situ are formed.

The use of the antistatic according to the invention is advantageous By means of thermoplastic polymer materials,

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such as those involved in the addition and interpolymerization of Compounds with ethylenic double bonds are obtained. Such polymer materials include, for example, polyolefins such as Homopolymers of ethylene and propylene, and copolymers of ethylene and propylene with one another or with higher aliphatic ° C olefins and also the aromatic polymers Vinyl compounds. Particularly valuable antistatic • agents are obtained through use with the last-named polymers obtained, to which e.g. polystyrene and copolymers of styrene with methyl methacrylate or acrylonitrile, including in the presence of rubber reinforcing materials or by subsequent mixing with these rubber reinforcing materials produced polymers, such as polybutadiene and rubber-like butadiene-styrene / copolymers,

In the case of the antistatic agents preferred according to the invention, the weight ratio of the sulfonate to the amide 6: 1 to 2: 1.

The sulfonate component of the antistatic agent can be found in thermoplastic Polymerizate material will be present within a wide range of concentrations, but will range from 0.1 to 3.0% by weight, based on the polymer with which it is used, is preferred. The preferred range is at Polyethylene 0.1 to 0.5 $, for polystyrene 1.0 to 3.0 #.

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Ao

As is known, the amount of in an antistatic FoMhman:; e required antistatic additives of factors,

/to the ·

such as the level of protection desired, the properties of the the specific deformation level that is applied and the humidity of the atmospheric environment. Using of the antistatic agents according to the invention for generally applicable preparations based on aromatic vinyl polymers are usually not less than about 2 wt. of antistatic agent, based on the mixture, used. ^ an unnecessarily large amount of the antistatic additive should be used be avoided in order to keep the changes in the basic properties of the thermoplastic material as low as possible. Total amounts of the antistatic additive of 2.0 to 5.5 #, especially 2.5 to 5.0 $, are preferred.

In the application that is still pending, there will be an antistatic Agent composed of an alkanolamide of an organic acid and an oxide, hydroxide, carbonate, bicarbonate or carboxylate of " Ammonium or a group IA or IIA metal of the periodic System as a means of avoiding discoloration

f wrote. Such means of preventing discoloration can

in the antistatic agent according to the invention, preferably in

Quantities from 1 to 20 wt .- ^, based on the weight of the other

■■■■■■ ■; ■ - ■ -.- ■ '' - ■ -: ■; :, -4 essential amide, are present. Hydroxides, carbonates, bicarbonates and stearates of sodium, potassium, magnesium and calcium are preferred as such agents.

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QRiBlNAl.

A polymer material, since the antistatic according to the invention Contains agents, conventional polymer additives, such as lubricants, antioxidants, pigments, for example and contain dyes.

Incorporation of the antistatic agent into the thermoplastic Polymerization is usually carried out by adding the antistatic agent when the polymer exists in the molten state. Will be the antistatic agent formed in situ in the polymer with which it is to be used, so first one and then the other component ^ of the antistatic agent can be added to the polymer. It is useful to have both components with the polymer in one Mixing device or in the cylinder of an extruder from which the polymer is extruded to mix. That Antistatic agents or the components of the same can be added to the polymer as a solution in a volatile solvent, such as E.g. water that is later, for example, at the opening of the extruder removed, added.

Polymers containing the antistatic agent according to the invention, have excellent antistatic properties and can be molded at high temperatures by injection molding, without the moldings obtained being discolored. Above it ^ iinaiis vrarle found that polystyrene preparations containing antistatic agents have excellent flow properties and therefore no conventional lubricants such as mineral oils or butylstones

00983Α / 17Θ7

"I,

arat, must be admitted. This is a particular advantage of the preparations according to the invention, since the addition of such conventional Lubricants lower the softening point of the polystyrene, whereas the antistatic agents according to the invention do not significant decrease in the softening point of polystyrene cause.

The following examples serve to further illustrate the invention

Example 1

A mixture of 93 »4 parts consisting of toughened polystyrene (" Styron 492 D ", manufactured by the company Distrene Ltd ^ and a concentrate of ultramarine-blue pigment in polystyrene was shaken with 0.7 part of molten lauric diethanolamide the coated polymer granules with a powder mixture of 2.0 parts of sodium dodecylbenzenesulfonate ("SDD-powder TTo. 1"} Associated Chemical Companies Limited), 0.2 parts of calcium carbonate, 0.2 parts of silicon oxide ("Monosil VN.3 ¹¹ , filler ( The resulting mixture was extruded and processed into tablets; for comparison, three polymer preparations were made with 2.7 parts of lauric diethanolamide as the only antistatic agent or with 2.7 parts of sodium dodecylbenzenesulfonate as the only antistatic with ⁴ el or manufactured without an antistatic additive.

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The following table gives the flow properties and softening points of these polymers.

Table I.

Antistatic laurine diethanolamide ¥> 3 0 0, 7th 2 0 2 , 7 Additives Sodium dodecylbenzene
sulfonate, $ 95 0 2, 0 5 , 7 0 ' Melt Flow Index, ASTM D 1238,
Condition G, s / 10 min. , 5 6, 3 95 ,8th 6th , 5 Softening point, BS 2782-1020, ⁰ C. , 5 94 * Ul 85 , 5

From this table is the excellent combination of river and heat resistance properties when using the present invention antistatic agent clearly evident.

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W.

The polymer preparations were made into wedge-shaped objects by injection molding using a screw preplasticizing device, their cylinder to a temperature of

ο - ■ ^!

260 0 was used. The moldings from preparations;

the antistatic agent according to the invention or Laurindi-! Ethanolamide alone or containing no antistatic additive, were all white, in contrast to the discolored form- ' bodies that have sodium dodecylbenzenesulfonate as the only antistatic agent contained.

Using the same apparatus, the preparations were then used to make cups. The cups are sprayed with soot to determine the level of static build-up on their surface. The cups that the

Antistatic additive mixture and sodium dodecylbenzenesulfonate as the only antistatic additive contained «were shown no patterns of attracted soot dust. The cups with Laurindiilthanolamid as the only antistatic additive little attracted dust, while the cups without antistatic additive were largely covered with dust patterns.

Example 2

/it

Using a similar procedure to the example above is described, the same components were used in the manufacture of some preparations with different proportions of sodium dodecylbenzenesulfonate and lauric diethanolamide. However, a conventional lubricant (dimethyl phthalate) in an amount of 1% by weight based on the final preparation. The following table shows the properties of these preparations.

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T * b t 1 1 β

ω co ω

antistatic
Allowances Lauric diethanolamide, Ί
Sodium dodtoylbeneol
■ sulfonate, < 0
0 2.5
0 0.5
1.5 1.0
1.5 0
2.0 0.5
2.0 0
2.5 σ Sohaelifluflindex, Λ.3.Τ.Μ. D 1238,
Condition ft, ρ / 10 min 5.9 11, 2 8.2 9.6 7.2 8.8 7.9 Softening point, B.S. 2782
Method 102 C, 92.5 82 91 89.5 92 91.5 92 Extent of S uptake
(see below) A. B. C. σ C. G

A ■ strong B »slightly C» negligible

/ ffc

The table clearly shows the excellent combination of flow and heat resistance properties when using the

antistatic agent.

The Polvmerisatpräjjarate were used for molding ~ ψ6π cups under the conditions described in the above example .. The cups were sprayed with fine red dye stinmen to the extent of statistical charge on their surfaces to .toe ". '"

The above table shows the extent of the dust pick-up.

It can therefore be seen that the use of the antistatic agents according to the invention leads to excellent antistatic properties without discoloration.

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Claims (1)

1. Antistatic agents for polymeric materials, thereby the end
characterized in that they consist of a large proportion by weight of alkyl, aryl or alkaryl sulfonate and a small proportion by weight of alkylalkanolamide or hydroxypolyalkoxyamide. 2. Means according to claim 1, characterized in that the Sulfonate an alkyl sulfonate with an alkyl chain length of about 6 to 22 carbon atoms, an alkyl benzene sulfonate with an alkyl chain length of about 6 to 22 carbon atoms, an alkyl naphthalene sulfonate having one or two alkyl groups each having a chain length of about 1 to Carbon atoms or a mnaphthyl methane are preferred with one or two alkyl groups of one chain length each is from about 1 to 4 carbon atoms » 3. Means according to claim 1 to 2, characterized in that then alkanolamide or hydroxypolyalkoxyamide is one such, which is derived from lauric acid. 4. Means according to claim 1 to 3, characterized in that the alkanolamide diethanolamide, preferably lauric diethanolamide, is. 009834/1767 / it a Polymer and an antistatic agent according to claim 1 to 4 contains. 6. Polymer preparation according to claim 5 »characterized in that the polymer is a homopolymer of ethylene or propylene, a copolymer of ethylene or propylene or a copolymer of ethylene or propylene with an aliphatic ° C olefin with more than 3 carbon atoms is. 7. -'polymerisatpräparat according to claim 5, characterized in that that the polymer is that of styrene or a copolymer made of styrene with methyl methacrylate or acrylonitrile is. . 8. polymer preparation according to claim 7, characterized in that that the polymer is one that is used as a reinforcing material Contains polybutadiene or a rubber-like copolymer of styrene and butadiene. 9. Polyraerisatpräparat according to claim 5 to 8, characterized in that the weight ratio of sulfonate zn alkanolamide or Hydro :: v-polyalkoxysrniä 5 r '/ s 6 ι'. up to 2 ; i btl- 009834 / ORIGINAL 10. Polymer preparation. According to claims 5 to 9 »characterized in that that the sulfonate component of the antistatic agent in an amount of about 0.1 to 3.0 wt .- ^, based on the polymer, is present. 11. Polymer preparation according to claim 10, characterized in that there's the sulfonate component in an amount from about 0.1 to 0.5 (rew .- ^ i, based on a polymer of ethylene present is. 12 polymer preparation according to claims 5'to 11, characterized - '■: "indicates that the antistatic agent is in an amount of about 2.0 to 3.5 <Jew .- #, based on the polymer, än- : ν, weaend is. V -. J ^, v ' 13 · Polymer preparation according to claim 12, characterized in -... "net containing about 0.5 to 1.5 wt .- # lauric diethanolamide and - _: about 1 * Ό to 2.0 wt .-% sodium dodecylbenzenesulfonate, each- :; Weila related to-, daö polymer, contains as an antistatic agent ^. ': ^; 7 14. Polymer preparation according to claim 5 to 13, characterized geke '-' naeichnat, that as a matter of course as a means sum? eraeiden γόη discoloration tin Oisyd, Hydroxyd. Carbonates bicarbonate odar Garboxylat? on Aaaaoni - '. ia »or ainea Metall dar G "i Λ or ^ r 2 A das ^" - iodiachen Sjatenss anthäl * - ;, The patent attorney ^Λ · 31 · Β34 / 1737 ^ ~ ^L