DE1234020B - Thermoplastic compounds made from polyolefins for the production of anti-static moldings - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4SSBTWWt PATENT OFFICE

EDITORIAL

Int. CL:

C08f

C08L 27/00

German KL: 39 b -22/06 / \

Number: 1234020

File number: C 34046IV c / 39 b

Filing date: October 8, 1964

Opened on: February 9, 1967

It is known that plastic objects, including those made of polyolefins, are antistatic can do by treating them externally with aqueous solutions of alkyl sulfates and sulfonates. The protection against electrostatic charge achieved in this way naturally only lasts as long as until the applied thin layer is wiped off or dissolved by the use of the objects. It is therefore preferred to incorporate suitable additives into the polyolefins before shaping, to for example polyglycol monoethers (British patent 731 728, Belgian patent 536 632), polyglycol monoesters (German patent specification 1159 637), polyglycols (French patent specification 1250 926), Fatty acid alkanolamides (British Patent 906174), alkylalkanolamines (U.S. Patent 2,992,199) and alkoxylated alkylenediamines (U.S. Patent 2,922,770). Albeit usually proportionately high proportions of these substances must be incorporated into the polyolefins in order to obtain sufficient Antistatic effect is obtained, so that the added substances in an undesirable manner to exudation tend, since one has limited oneself to these non-ionic additives. Nowhere is it suggested to incorporate ionogenic substances of the type of alkyl sulfates or sulfonates mentioned, apparently If only because of the introduction of an ionic compound into an extremely apolar system do not remain without repercussions on its mechanical properties or on individual features can and undoubtedly also have a marked influence on the behavior of the plastic during processing. For this reason, the incorporation of such ionic substances must appear to be pointless and harmful.

It has now surprisingly been found that thermoplastic Masses of polyolefins and sulfur-containing antistatic agents become excellent antistatic agents Moldings lead if they are antistatic 1 to 6 percent by weight at least one sulfonic acid salt, the organic radical of which is an alkyl group having 4 to 30 carbon atoms or a Alkaryl group with 2 to 30 chain carbon atoms or a polynuclear aromatic group with one to two alkyl groups of 1 to 9 carbon atoms each, optionally in a mixture with at least a known antistatic.

Suitable polyolefins, which can be made antistatic by incorporating the additives, are high pressure and low pressure polyethylene with molecular weights between 30,000 and 180,000, polypropylene with molecular weights between 200,000 and 7 (X) OOO and poly - «- butylene with molecular weight
Manufacture of anti-static moldings

Applicant:

Chemical works Hüls Aktiengesellschaft, Mari

Named as inventor:
Dr. Friedrich Seifert,
Dr. Konrad Rombusch,
Dieter Carla, Mari

Weight between 1,000,000 and 3,000,000, the same Copolymers of ethylene, propylene and / or butylene as well as mixtures of components this kind.

Suitable sulfonic acid salts are obtained by sulfurizing mononuclear alkyl-substituted aromatics, whose alkyl radicals contain 1 to 30 carbon atoms, or by sulfurization of a polynuclear (isolated or condensed) aromatic, which one contains up to two alkyl groups of 1 to 9 carbon atoms each, or by reacting a paraffin with 4 to 30 carbon atoms with sulfuryl chloride, and in all cases by subsequent neutralization of the compounds obtained by means of a base as in the case of the alkyl sulfates. - Suitable are e.g. B. Sodium tetrapropylene benzene sulfonate, Potassium n-dodecylbenzenesulfonate, bis - (diisobutylmethyl) - naphthalenesulfonic acid Triethanolamine or potassium 2-methyl-5-isopropyldiphenylsulfonate, Calcium undecen- (10) -ylbenzenesulfonate or diphenylmethane-4-sulfonic acid Sodium.

In order to achieve the desired anti-static effect, one of these compounds can be used or use several, also mixed from different types. One achieves in either case an increasing effect with an additional amount of 1 to 6 percent by weight.

Surprisingly, however, it has now been shown that both the type of polyolefin used and its Processing method for the optimal dosage of the additives play a decisive role.

It has been found that 1 to 3 percent by weight of the sulfonic acid salts are then most advantageous added when the polyolefin mass in the extrusion process including deep-drawing and blow molding want to use, for example with the

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3 4

Production of extruder, calender, blown or, finally, it has also been found that anti-electric flat films as in general any extruder - static polyolefin masses special and not pre-profiles, where in the case of a tube there are also advantages to be seen, which 1 to 5 Ge inflation, in the case of a film, a deep-drawing process based on weight percent of a mixture of 5 to 95 percent by weight can be. Dosages at the lower 5 parts of the sulfonic acids have salts on the one hand and Limit apply above all to high-pressure poly- on the other hand from 95 to 5 parts by weight of one or ethylene, dosages on the upper one for highly crystalline several well-known antistatic agents of the general formula lines, possibly also heavily pigmented

Low pressure material including interpolymer- RjO (CH ₂ CH ₂ O) »H a

seeds based on ethylene-butylene, ethylene-propylene to

or propylene-ethylene with up to about 10 mol each where R _{1 is} an alkyl, alkenyl, acyl or aralkyl

percent of in a smaller amount in the copolymer group with up to 20 chain carbon atoms or

other monomers present. It is especially hydrogen and η is a number from 2 to 100, or it is noticeable that a copolymer, even if it

is less crystalline than its main polymer «5 / R3

component alone would be, often a higher dosage R ₂ ν b

requires; this contrary to the expectation- \

thing means that it is appropriate to use a higher ⁴

Density and crystallinity of a homopolymer a ^{0 (} fcr

choose a slightly higher addition, while vice versa 20 rows R ⁷

but a lowering of the crystallinity by incorporation \ ^ ^ N c

another component from the homologous series / \

of the α-olefins in the polymer chain no lowering Re R ⁹
which makes antistatic concentration beneficial. at

Extruder articles is below 1 percent by weight of the 25 wherein R _{1 is} an alkyl, alkenyl or acyl radical with 6 to

Additions of the effect insufficient, above 6 weight- 30 carbon atoms, R ₃ , R ₄ , R ₆ , R “R ₇ and R ₈ one

percent structures appear on the surface, - (CsHisO ^ H group with χ - 2 or 3, η = 1 to

in addition, flow and output are adversely affected 30, R ₄ , R «and R ₈ also represent a hydrogen atom and X

or the extrusion at all called into question. is an alkylene chain of 2 to 6 carbon atoms.

It has also been found that these per se known antistatic additives in the compression molding process with 3 to 6 percent by weight of the sets are of a nonionic nature.
Additives give the best results. The compounds R ₁ O (CH ₂ CH ₂ O) _n H, in which Rj, for example, press plates are produced which - and an alkyl, alkenyl, acyl or aralkyl group with it is particularly important - no further deformation up to 20 chain carbon atoms or the hydrogenation process, have doses below 35 and a number from 2 to 100, half 1 percent by weight does not result in a sufficient anti-electro-simple addition of ethylene oxide to the static effect of ethylene; arise, or the aging values are reduced and the mechanical, aliphatic, saturated or unsaturated alcohols, in particular tensile strength and limit bending stress with 6 to 20 carbon atoms or alkylphenols, are considerably reduced. A do- 40 or naphthol, the alkyl radical of which consists of 1 to 20, preferably more than 6 percent by weight, also has 6 to 18 carbon atoms, whereby the electrostatic ether does not arise from the type characterized above, and more valuable advantages, so that the range between 3 and carboxylic acids, especially fatty acids, with ent-6 percent by weight, the optimum of these processing-speaking monoesters, whose molar technology represents. However, if the plate material is then further deformed within wide limits between 2 and 100 mol, ie deep-drawn ethylene oxide per mol of alcohol, phenol or acid, then the dosage may apply in this case. Suitable are e.g. B. Polyethylene glycol anti-electrostatic equipment, the information given above for extruder 4000 (number means the molecular weight), nonyl profiles, that is, one obtains from phenylheptaethylene glycol, stearoyl polyethylene glycol granulate or agglomerate starting from a non-50 kol-1550, intermediate laurylhexaethyleneglycol to be anti-electrostatic, oleyldodeca ethylene glycol, 1,5-dimethyl - ^ - naphtholtriethylenglyprodukt an anti-electrostatic end product, whereupon kol or 4-oxydiphenylmethane hexaethylene glycol.
it finally matters. Here, too, the connections apply
with regard to density or crystallinity, type of polymer and an additional use of neutral 55 R ₃
Substances already said during extrusion. /

Similarly, it was found that in the case of the ² \

Turning the polyolefin masses in injection molding, rotational R ₄

casting and bulk sintering process the additional amounts of as well

2 to 4 weight percent is most advantageous; 60 ^ ^ ₇
The same applies to cast and flat films based on ⁵ \ /
low molecular weight polyolefin types. Below 1 Ge • N - X - N.
weight percent the effect is unsatisfactory, and from R ₈ ^ R ⁸
6 percent by weight, there is a strong tendency towards increased stress cracking, with internal 65

half of this range, the abovementioned steps in which R _{2 is} an alkyl, alkenyl or acyl radical with 6 to

Specifications relating to the density and type of polymers 30 carbon atoms, R ₃ , R ₄ , R _s , R _e , R ₇ and R ₈

are valid. a - (C _x H _2a; O) »H group with χ = 2 or 3, η = 1

5 6

to 30, R ₄ , R ₆ and R _{8 are} also a hydrogen atom and X is a concentration range of importance. In particular, if an alkylene chain with 2 to 6 carbon atoms is present, mixtures of this type have a conventional effect, either by alkoxylation of acidic printing processes and using amides of saturated or unsaturated carboxylic acids of the printing inks developed for normal polyolefins with between 30 and 6, preferably 20 and 10 Carbon - 5 compared to the use of the individual components of substance atoms or by reaction of acid chlorides, greatly improved adhesive strength of the print, and with mono- or dialkanolamines; Here, the addition of ionic number of possibly existing or subsequently incorporated compounds, the stress cracking behavior of anti-electrostatic alkoxy groups per Η atoms of the unsubstituted polyolefin mixtures of neutral substituted amide radicals can be between 1 and 30. To influence ge io favorably,
Also suitable is the alkoxylation of the amines, which can be obtained by hydrogenation of the CO groups of the material, which is present in powder form, by means of terized starting amides or by Hoffmann's cold kneading and subsequent dry breakdown of the granules, likewise the reaction by halogenation. In the case of solid or semi-solid products alkanes with mono- or dialkanolamines, the addition of what has already been said above can also apply in dissolved form in groups per Η atoms for 15 and to achieve a quick and good result. The alcohol, water, etc. entered and the solvent compounds based on alkylenediamine are finally evaporated medium afterwards,
is obtained by alkoxylation of by two to The polyolefin compositions can contain pigments, fillers, six CH ₂ groups linked, terminal amino dyes, plasticizers and stabilizers groups or from corresponding ω, ω'-dihalogen or antioxidants, the Influence compounds by reaction with mono- or di- in particular of pigments on the antielektrostaalkanolaminen, whereby here too with regard to the number tables effectiveness of the sulfonates or on the mixtures containing these possibly present or subsequently incorporated is considerably lower than alkoxy groups the same as with the Amides applies. 25 this particularly suitable when using neutral compounds are z. B. lauric acid diethanolamide, oil special of polyethylene glycol derivatives is the case, acid diethylene glycol amide, hexadecyl-N-diethylene glycol, which is an additional advantage. The beankol -N -ethanolamide, Ν, Ν, Ν ', Ν' -Tetrahydroxyäthyl- claimed antistatic polyolefin compositions allow ethylenediamine, Ν, Ν'-dihydroxypropylhexamethylene- without difficulty in the alldiamin for polyolefins. 30 common range from 120 to 35O ⁰ C according to the

Process these non-ionic compounds as an additive to various process technologies.

the sulfonates offer the essential advantage that to assess the antistatic behavior

the limits for the various processors are new masses besides metrological findings

procedure are to be drawn, no longer observed (see Tables I and II) a simple hand test, which as

will need. 35 dust test is extremely revealing.

For example, in the case of a polyolefin composition This dust test is judged as positive when intended for extrusion and is highly pigmented, at 50 ° / ₀ relative humidity and 23 ⁰ C, a grated with a ie about 2 percent by weight of inorganic pigment cotton cloth specimens in 1 limit without the use attracts no more ash particles ^- contains cm distance, the 3 ° / o leaves. For a proper use of the non-ionic additives, just adhere to the 40 right assessment is the observance of the air humidity, if one attaches importance to good processing; Due to the fact that, above all, the electrostatic use of non-ionic additives, this charge is strongly influenced and the disregard of which easily eliminates the difficulty, which, in addition to the possibility of incorrect judgments, can be particularly important.
In Table I, for some anti-electrostatic lowering of the dosage is possible. 45 mixtures using an alkyl sulfonate

The same applies to the other use mixtures with an average chain length of 15 carbon

purposes, for which the limits of the optimal effect, the results of these dust test

and processability by adding the non-ionic method are given, as are the respective values of the

Connections are canceled. Surface resistance according to DIN 53482 with

The advantage of mixtures of anion-active and 50 gave over the decay by rubbing with one

Neutral substances is not only using the charge generated by the cotton cloth side

the sulfonates, but also from the neutral side of the measuring head of the field strength meter

Connections are given, because on the one hand a swivel hanger (Textilpraxis, 12/11, p. 1147,

additional introduction of sulfonate also here a 1957) with simultaneous consideration of the

Lowering the dosage, which is particularly important in the case of processing methods. In the "Comments" section

When compounds of the type are used, those dealt with at the outset can be found with the addition

caused effects listed.

R ₁ O (CH ₂ CH ₂ O) _n H It can be seen that the production of flawless,

Anti-static foils (extruder, blown and flat foils are important, and on the other hand, those with stick foils), anti-electrostatic deep-drawn parts and compounds containing substances, even with low hollow bodies when using low-pressure poly dosages, the strong exudate ethylene of the specified characterization A range of 1.5 to 2.5%> less good but below 1 is practically eliminated by the addition of sulfonate. The mutual influence of the Kompo- and above 3 ⁰ I ₀ , is possible. In the case of injection molded parts, it is therefore necessary to look from both sides, and this most favorable range between 2.5 _{% is active for both the neutral and the anionic and 3.5 ° / 0} , less below 2 or above 4%, is active Connections of great advantage and thus in the case of press plates, on the other hand, between 3 and 6%> in the pre-mixing of such components in the total lying case from 4 to 5%.

Table I.

Weight percent Surface resistance Moldings and characterization of the starting material Characterized sulfonate in ΜΩ Column 6, middle (50% relative humidity / 23 ° C) Films (extruder, blown and flat films) 0.1 to 0.9 ² ) 10 ^e Deep-drawn parts and hollow bodies LP polyethylene including ethylene propylene 1.5 to 2.5 10 * or butylene copolymers η-reu ' approx. 1.6 to 3 6.1 to 8 10 ⁴ (c = 0.1 in p-xylene at HO ⁰ C) Bulk density: about 0.940 to 0.955 Injection molded parts, rotational molding as well as flat or cast 0.1 to 0.9 ² ) 10 ^e foils off LP polyethylene including ethylene propylene 2.5 to 3.5 10 ¹ or butylene copolymers η-τβά- about 1.2 to 2 6.1 to 8 ² ) 10 ⁴ Bulk density: about 0.958 to 0.960 Press plates from 0.1 to 0.9 ² ) 10 « LP polyethylene including ethylene propylene - 4 to 5 10 * or butylene copolymers jy-reci: about 1.6 to 3 6.1 to 8 ² ) 10 ⁴ Bulk density: about 0.940 to 0.955

^x ) The expression: »slowly« = the half-life of charging is greater than 4 minutes.

"Rapid" = the half-life of the charge, which has been reduced by several times, is within 1 minute.

Table II

Surface resistance in ΜΩ
(50% relative
Humidity / 23 ⁰ C)

Fade away

of charging

(50% relative

Humidified) ¹ )

1. Polypropylene-O-sample »y-red: 2 to 5

(c = 0.1 in p-xylene at 110 ⁰ C) bulk density: 0.901 to 0.907 ² )

2. -f 3 to 5 percent by weight of laurylheptaethylene glycol or nonylphenylheptaethylene glycol ² )

3. -j- I to 3 percent by weight oleic acid diethanolamide or heptadecyl diethanolamine or Ν-, Ν-, Ν ', Ν'-tetrahydroxyethylethylenediamine

4. + 0.5 to 1 percent by weight of lauryl heptaethylene glycol H- 0.5 to 1 percent by weight of nonylphenylheptethylene glycol H- 2 to 1 weight percent sulfonate

5.H- 0.5 to 1 percent by weight of lauric acid diethanolamide or hepta-

decyl diethanolamine or Ν, Ν, Ν ', Ν'-tetrahydroxyethylethylenediamine
H- 2 to 1 weight percent sulfonate

6. Polyethylene (according to Table I)

H- 0.5 to 1 percent by weight of laurylheptethylene glycol H- 0.5 to 1 percent by weight of nonylphenylheptethylene glycol H- 2 to 1 weight percent sulfonate

7. Polyethylene (according to Table I)

H- 0.5 to 1 weight percent dodecyl diethanolamine H- 2 to 1 weight percent sulfonate

^l ) See note in Table I. ² ) Comparative tests.

10 '

10 «

10 ⁴

5-10 ³

5-10 ³

5-1Ο ³

slow

Border fast / slow

quickly

quickly

quickly

quickly

quickly

ίο

(sole use of sulfonate) Dust test
(50 ° / »relative humidity / 23 ° C) Remarks Decay of the charge ¹ )
(50Vo relative humidity / 23 ⁰ C) - a) Insufficient anti-static equipment slow -I- + b) anti-static without those listed under c)
disadvantage
c) Structures on the surface, bad rheological
gical behavior: uneven flow and out
push quickly
quickly - a) Insufficient anti-static equipment slow b) anti-static without those listed under c)
disadvantage
c) Worsened barking test or greatly increased tendency
poor processability for stress cracking quickly
quickly ⁺ a) Insufficient anti-static equipment
b) anti-static without those listed under c)
disadvantage
c) heavily modified mech. Property profile, esp
special severely reduced tensile strength and
Limit bending stress slow
quickly
quickly

*) Comparative tests.

(Sulfonates together with neutral components)

Dust test
(50 ° / ₀ relative
Humidity / 23 ⁰ C)

Suitable for making

Remarks

natural-colored as well as colored moldings after the injection molding and extrusion process for the production of slot, blown and flat films as well as press plates

natural-colored as well as colored moldings after the injection molding and extrusion process for the production of slot, blown and flat films as well as press plates

as under 4

as under 4

as under 4

Adversely affect additives in this order of magnitude required for an antistatic effect strong flow behavior, show increased stress whitening, streaking and sometimes a deterioration in color number

Adversely affect additives in this order of magnitude required for a sufficient effect strong flow behavior, lead to strongly adhesive surfaces, evident deterioration in color number and intense brown discoloration when exposed to high temperatures

The masses have good flow behavior, the moldings have smooth, shiny, non-sticky surfaces, compared to 2, they show reduced stress whitening and no deterioration in color number

The masses have good flow behavior, the briquettes are smooth, shiny and completely tack-free Surfaces with only a slight deterioration in the color number when exposed to high temperatures (cf. 3)

The masses have good flow behavior, the briquettes are smooth, shiny and completely tack-free Surfaces with no deterioration in color number

The masses have good flow behavior, the moldings have smooth, tack-free surfaces with only slight deterioration in color number (cf. 3)

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Table I shows polypropylene (Examples 1 to 5) and polyethylene (Examples 6 and 7) - valid for general-purpose as well as special types - the superiority of such masses, the contain both sulfonates and neutral antielectrostatics, which on the one hand are those shown in Table I. Limits disappear, on the other hand also the obvious superiority of such mixtures of the sole application of neutral compounds becomes visible, e.g. B. on the comparison of Examples 2 and 3 with 4 and 5 and Example 6 with Table I. The same alkyl sulfonate mixture was used As in Table I. In principle, the same results are obtained if the anionic compounds in Column 2 listed compounds and instead of the neutral substances listed in Table II the in Compounds marked in column 4 are used.

Such results cannot be achieved if similar test specimens made of low-pressure polyethylene and polypropylene, but which do not contain an antistatic, are immersed in a 2% aqueous solution of the sulfonate used in the preceding examples and allowed to dry. The surface resistance of such samples is around ΙΟ ⁴ ΜΩ, the charge dies down quickly, and the test specimens rubbed with a cotton cloth do not attract any dust particles. But after washing it with water once, the charge only ^{subsides slowly, the surface resistance reaches values of up to 10 β} ΜΩ, and the ash test becomes negative.

It can be seen from this that a surface treatment of polyolefin bodies with, for example Alkyl sulfonates acts as long as the polyolefin bodies are not affected. Already a one-time Water treatment, as used in household items, toys and most technical products is always possible or even inevitable, the antistatic equipment can come in handy completely eliminate.

Claims (1)

Claim: Thermoplastic compositions made from polyolefins and sulfur-containing antistatic agents for the production of antistatic moldings, characterized in that that they are used as antistatic agents 1 to 6 percent by weight of at least one sulfonic acid Salt, the organic residue of which is an alkyl group having 4 to 30 carbon atoms or an alkaryl group with 2 to 30 chain carbon atoms or a polynuclear aromatic group with one up to two alkyl groups of 1 to 9 carbon atoms each, optionally in a mixture with at least one known antistatic. Considered publications:
German Auslegeschriften Nos. 1 034 849, 1 154 268, 174 739;
British Patent No. 847 106. 709 508/355 1.67 © Bundesdruckerei Berlin