DE2005854B2 - ANTI-ELECTROSTATIC THERMOPLASTIC MOLDING COMPOUNDS FOR THE PRODUCTION OF MOLDED BODIES - Google Patents

Description

wherein R is an alkyl or alkenyl radical having 6 to 26 carbon atoms, R ₁ and R _{2 are} the radical

(C _x H _2x O) _n H

with χ = 2 or 3 and η = 1 to 7, R ₂ also denotes hydrogen and ζ = 0 or 1, are replaced.

The invention relates to antielectric molding compositions and molded articles made from polyolefins, the fatty acid glycerides and glycerin.

It is known to incorporate thermoplastic materials such as polyethylene at the same time as 3 to 20 percent by weight of an adder material in the form of a pigment or filler, polyhydric alcohols or fatty acid glyceride (US Pat. No. 2,758,984). It is also known from German Auslegeschrift 1 271 391 to mix polyolefins to prevent fogging in films with mono- and diglycerides which contain less than 1.5% glycerol. Finally, it is also known to use fatty alkyldialkanolamines to make polyolefins antistatic, both on their own (US Pat. No. 2,992,199) and in combination with other antistatic compounds (German Auslegeschriften 1230 210, 1 234 020).

The use of polyhydric alcohols, such as. B. glycerin, is in view of an antistatic effect - as will be shown - completely unsatisfactory. By contrast, glycerol esters behave very differently.

The German CiT ^ legungsschrift 1 927 677 can be seen that the monoglycerides of saturated C _{12 to} C ₁₈ fatty acids can be used as antistatic agents, but have no noticeably good effect. In order to obtain particularly effective monoglycerides, this German laid-open _{specification proposes the use of C 6} to Q 0 fatty acids and shows that such products should be contaminated as little as possible by glycerol. For this reason, a process for the production of 100% pure monoglycerides is also specified.

Fatty alkylalkanolamines remain practically completely inactive at concentrations below 0.2 percent by weight. At most with high pressure polyethylene is one

ίο determine low effectiveness. In contrast, at higher dosages, namely> 1%, they cause sticky, oily, greasy deposits on the surfaces of the fittings. Combinations with other anti-static compounds are therefore a real necessity.

For various reasons it is desirable to utilize the crude reaction products, some of which contain a lot of glycerol, of glycerol on the one hand and longer fatty acids or their natural triglycerides on the other hand, although there is a prejudice against the use of glycerol-rich mixtures and against the use of longer-chain fatty acid glycerides from the prior art consists.

This task becomes surprising with anti-static Molding compounds dissolved by the fatty acid glycerides for the production of molded articles from polyolefins and glycerol contain according to the invention solved in that these 0.2 to 2.8 percent by weight, based on the molding compound, a mixture of

• * ° a) 60 to 96 percent by weight of glycerol monoester of a fatty acid with 12 to 26 carbon atoms, the di- and triester content of which is at most 25 percent by weight of the glycerol-glycerol ester mixture, and
b) contain 40 to 4 percent by weight glycerol.

0.05 to 0.8 percent by weight of the mixture consisting of a) and b) can according to a special Embodiment of the invention by

c) an alkoxylated amine of the formula

R- (OCH ₂ -CHOH-CH ₂ J ₂ -N

be replaced, in which R is an alkyl or alkenyl radical having 6 to 26 carbon atoms, R ₁ and R _{2 are} the radical

(C _x H _2x O) _n H

with x = 2 or 3 and η = 1 to 7, R ₂ also denotes hydrogen and ζ = 0 or 1.

Suitable polyolefins which can be made antistatic by the additives are, for. B. high and low pressure polymers of ethylene, propylene, butene (l), pentene (l), etc., especially all types of polyethylene with »/ _red values of about 0.4 to 4.0, corresponding to average molecular weights of about 20,000 to 200,000, polypropylenes with; / _r) , _d values of about 1.5 to 7.0, corresponding to average molecular weights of about 150,000 to 700,000 and polybutene- (l) with i _lred values of about 1, 0 to 6.0, corresponding to average molecular weights of about 500,000 to 3,000,000, which are obtained according to known process technologies (see R. V ierweg and A. Müller, Kunststoffe-Handbuch, Vol. IV, Karl-Hanser-Verlag, Munich 1966 ) getting produced,

as well as any mixed polymers and polymer mixtures thereof.

The total content of the antistatic mixture is 0.2 to 2.8 percent by weight, preferably 0.4 to 2.0 percent by weight.

As component a) of the mixture of a) and b), which alone or in a further mixture with the Component c) is used, one uses the monoester of glycerol and fatty acids from 12 to 26 carbon atoms, especially 12 to 18 carbon atoms, especially 14 carbon atoms. These monoesters can - for example from their production ago - still contain minor proportions of di- and / or tri-esters. These should, based on the mixture of a) and b) does not exceed 25 percent by weight. You put the component a) in a Amount, based on the total amount of antistatic substance from 0.2 to 2.8 percent by weight (of which 0.05 to 0.8 percent by weight may consist of component c)), from 60 to% percent by weight, preferably 70 to 90 percent by weight.

The glycerine [component b)] is used antistatic in an amount based on the total amount active substance from 0.2 to 2.8 percent by weight (from the 0.05 to 0.8 percent by weight Component c) may consist), from 40 to 4.0 percent by weight, preferably 30 to 10.0 percent by weight, a.

One or more oxaikylated amines of the formula are used as component c)

R - (OCH ₂ CH ₂ OHCH ₂ ) ^ N

where R is an alkyl or alkenyl radical having 6 to 26 carbon atoms, preferably 10 to 18 carbon atoms, in particular 10 to 14 carbon atoms, R ₁ and R _{2 are} the grouping (C _x H ₂₁ O) _n H with χ = 2 or 3, preferably 2 , η = 1 to 7, preferably 1 to 2, and R ₂ also denotes hydrogen and z = 0 or 1.

This component c) is used within the total amount of anti-static additive (0.2 to 2.8 percent by weight) in amounts of 0.05 to 0.8 percent by weight, preferably 0.1 to 0.5 percent by weight, a.

The antistatic glycerine-glycerine ester combinations are obtained either by glycerolysis of fats and oils, or one starts with the reactants present in anhydrous form, Glycerin and fatty acid.

For example, with an approximately 7 to 8-fold molar excess of glycerol, these are heated to approximately 200 to 220 ° C (H un Deshagen, J.pr. (2) 28, 225) or the Na or K salts of such fatty acids are added with an α- or / f-halopropylene glycol (see, for example, G uthe, ZB 44, 83) and then add the required amount of glycerine at the end. Useful fatty acid components include: arachidic acid, eicosanecarboxylic acid, behenic acid, lignoceric acid and, in particular, lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid or glycerides containing corresponding amounts of glycerol, or />'- or (u + / i) -glycerides: / i-mono arachin, / f-monobehenate, u-lignocerin, especially fl-monostearin, ß-monostearin, (α + / J) -monostearin, α-monopalmitin, (α + / i) -monopalmitin, a-monomyristin, a-monoolein, (a + ^ -monoolein, as well as mixtures of these such as (α or β or α + /?) - monostearin / monopalmitin or (α or β or α 4- 0) -monostearin / monoolein or (α or β or a + β or α + ßV monopalmitin / monostearin / monoolein or (α or β or α + / O-monolauria / monomyristin.

Suitable amines [component c)] are obtained in

ίο case of ζ = 0 by oxyalkylation corresponding Amines, which are obtained, for example, either from alcohol via the haloalkane or haloalkene, or have also been synthesized via a Hofmann acid amide degradation - in the case of ζ = 1 by Addition of corresponding alkoxylated primary or secondary amines to glycidyl ethers of the general type formula

R OCH,

CH ■ CH ₂
O

with an alkyl radical R which corresponds to the definition given above.

There is no need for any particular indication that, in principle, several representatives of this class of substances can also be used at the same time. Suitable amines are e.g. B. Hexacosylaminomonoethylene glycol, nonadecyl-N - ((i - oxäthyl) - aminodiethyleneglycol, hexadecylaminotetraethylene glycol, decylaminoheptaethylene glycol, undecen- (10) -yl-aminopentapropylene glycol, N - (3 - - decyloxy), N - (3 - decyloxy - 3-Nonadecyloxy-2-hydroxypropyl) -N-diethanolamine, and in particular dodecyldiethanolamine, tridecyldiethanolamine, pentadecylmono- or -diethanolamine, heptadecylmono- or -diethanolamine, octadecyldiethanolamine, N- (3 -dodecyloxy) -hydroxypropyl) - (3-Dodecyloxy - 2 - hydroxypropyl) - diethanolamine, N - hexylaminotetradecylethylene glycol.

The antistatic substances are expediently incorporated into the powder present polyolefin, for example with the help of a simple mixer. The resulting mixture is then either directly or after previous compression to granulate the processing machines abandoned and deformed here in the temperature range of 120 to 300 C applicable for polyolefins. To ensure a good and quick distribution to achieve is sometimes the introduction of the antistatic compounds in solution Shape beneficial. One can also incorporate the antistatic agent into the polyolefin directly on the roller or z. B. perform injection molding in an extruder.

The method of first producing a granulate with a high concentration of antistatic agents has also proven itself and this during processing by adding granules free of additives to the desired content to bring antistatic.

You can add other additives that are otherwise common in plastics processing, e.g. B. dyes, stabilizers, plasticizers, extenders and fillers as well as lubricants.
Usual stabilizers are phenolic antioxidants such as. B. 2,2'-thio-bis (4-methyl-6-tert-butyl-5-octylphenol) (0.1 to 0.2 percent by weight), optionally together with sulfur-containing compounds such as dilauryl thiodipropionate.

It can also be expedient to add additional substances to the polyolefin, which one for longer Prevent slight yellowing of the amine component from the effects of high temperatures.

Such stabilizers are, for. B. Ester der phosphorous acid, especially didecylphenyl phosphite, decyldiphenyl phosphite, triphenyl phosphite, Tris - (nonylphenyl) - phosphite, Tris - (nonylphenol + 9 moles of ethylene oxide) - phosphite, which in quantities from 0.01 to 0.4 percent by weight, based on the polyolefin, can be added. An addition of alkanesulfonates, e.g. B. pentadecansulfonsaurem sodium, in the same way favorable. You need about 0.01 to 0.4 percent by weight for this, based on the polyolefin.

These additives usually do not affect the antistatic effect. If this should sometimes still be the case due to a very high filler content of chalk, glass fibers, asbestos, etc., a somewhat higher dosage of the anti-static additives can easily and quickly remedy the situation.

The anti-electrostatic behavior of the moldings is determined, among other things, by means of a simple hand test, which is generally used to assess the anti-static deterioration of finished goods and is referred to as the ash test for short. The result of this ash test is then viewed as positive (sign "+" it therefore refers to the effect of the incorporated substance), if at 50% relative humidity and 23 C from the vigorously rubbed object at a distance of 1 cm from the The surface on which the ashes rests, no more ash particles are attracted. They also mean Sign -: ash is strongly attracted; (-): ash is still attracted.

For a proper assessment, it is particularly important to pay attention to the air humidity, as it is has a particularly strong influence on the charging behavior.

It is surprising here that mixtures of a1 and b) give an excellent and reproducible antistatic effect within the claimed range. Above all, however, it is surprising that the glycerine,, velches is used on its own
is completely ineffective, is the decisive influencing factor in this synergism. It is also valuable that the amines (component c)], as a result of an additional synergistic effect, make concentration reductions possible compared with the amine-free glycerine-glycerine mixture.

In the following tables, what has been said about the synergism is clarified, namely first in Table I rectangular moldings made of partially crystalline, differently prepared propylene homo- and copolymers (Examples 2 to 20) both with each other and with the unfinished base material (0 samples in Example 1) compared. The procedure in tables (polybutene-! I)) and table III (polyethylene) is analogous. At the beginning there are always the 0 samples with information about the density and the? / _Rc , _d value of the polymer used, the reduced specific viscosity being based on c = 0.1 at 110 ^° C. in p-xylene.

In addition to the ash, the surface resistance (measured according to DIN 5343) and the decay followed by vigorous rubbing with a cotton cloth on the in a clamping device with the aid of a measuring head according to Sch wcnkhagen (see Textilpraxis 12/11, p. 1147 [1957]) suspended test specimens a generated charge are the most important criteria.

First of all, Table I shows that the high surface resistance and thus the charging behavior of the starting material (Example 1) can not be positively influenced by the addition of glycerol (Example 2). The use of glycerol monoesters can reduce the surface resistance,

ίο only to a very unsatisfactory degree (Examples 3, 4 and 6). Equally unsatisfactory results are also obtained if lauryl diethanolamine or N- (3-dodecyloxy-2-hydroxypropyI) -ethanolamine is used in a concept according to Example 13 on its own or in combination with glycerol or glycerol monoesters (Examples 14 and 15), although the somewhat more advantageous behavior of the combination with monoesters (Example 15) compared to that with glycerol (Example 14) analogous to Examples 2 and 4 also becomes clear here.

The results of Examples 16 to 18 are undoubtedly particularly surprising clearly about synergistic effects that - like example 18 shows - also due to the presence of as an impurity to be considered from the production Amounts of di- and tri-esters, which on their own also analogous to glycerol, are completely ineffective are not adversely affected, provided that their proportion in the glycerine-glycerine ester mixture does not exceed 25.

preferably does not exceed 20 percent by weight (comparative example 20). exceeds the glycerine content 30 to 40 percent by weight, based on the glycerol-glycerol ester mixture (Examples 7 and 19), so the overall effect of the combination is lost.

For optimal mixtures, the glycerine concentration should not exceed 25 percent by weight and not fall below 10 percent by weight of the glycerine-glycerine ester mixture.
If it is, in particular, below 4.0 percent by weight, an increased effectiveness compared to Examples 3, 4 and 6 can no longer be recognized.

Table 1 also shows that when the acrylic residues in the monoglycerides are compared with one another those with 12 and especially 14 carbon atoms are best (Examples 8 and 11). Higher fatty acid residues can also still be used (Examples 9 and 10). Compounds with too short fatty acid residues are of little use when glycerol is also used (Example 12).

The results can be found in Table II on the basis of Moldings made from polybutene (l) put together. It is noticeable that there is something here compared to polypropylene higher dosages are required to obtain results approximately in accordance with Table I. Again, Example 4, and in accordance therewith, Examples 7 and 8 show one clear synergism, which based on the findings of Examples 2 and 3 as well as 5 and 6 is a real element of surprise represents. It is understood from Comparative Example 9 that the presence is greater Amounts of glycerol analogous to Examples 7 and 19 of Table I has a negative effect.

Table III characterizes the behavior of differently prepared hollow bodies and blown

f> 5 foils made of a low-pressure polyethylene in the example 1 specific type. It can be seen that a consisting of 85% glycerol monolaurate and 15% glycerol Glycerin-glycerol ester mixture according to Example 4 of

7 8

Effect of the individual components (cf. with example 2 the terms and

and 3) is clearly superior and that combinations mean characters:

with amines of the type shown (Example 5 and 6) * _very , _m half-life> 120 ",

an additional lowering of the concentration slow half-life > 60 ". <120"

of additives allow in the case of the production of 5 ^ half-life> 10 ". <60"

Hachiblien (example 7) a total concentration _quickly half-life <10 "is sufficient,

tration already from 0.7 parts to 100 parts of the polymer ^{to lower the surface resistance to 10 9} ohms **) - = Ash is attracted to a large extent and thus a satisfactory antistatic (-) = ash is still attracted. To achieve behavior. io + = no ashes are attracted.

Table 1
Injection molded parts made of polypropylene

example Parts
on
KX) part
polymer 1 0 2 1.0 3 1.0 4th 1.0 5 1.0 6th 1.0 7th 0.5
0.5 8th 0.75
0.25 9 0.75
0.25 10 0.75
0.25 11th 0.75
0.25 12th 0.75
0.25 13th 0.1 14th 0.1 0.5 15th 0.1

0.5

Polypropylene: (injection molding types)

_{a) Propylene homopolymer} (D = 0.906, i hcd = 4) or

_{b) Propylene-ethylene copolymer} with 5 percent by weight of ethylene (D = 0.903, Vrcd = 4)

Glycerin

Glycerin (a) monomyristal

Glycerol (a) monostearate

Glycerin-fctj-monocaprylate

Glycerol (a) monolaurate

Glycerin (a) monostearate glycerin

Glycerin- (a) -monomvristate glycerin

Glycerine) a) monostearate glycerine

Glycerin (a) monobehenate glycerin

Glycerine (a) monolaurate glycerine

Glycerine-lal-monocaprylate Glycerin

Dodecyl diethanolamine or

N- (3-dodecyloxy-2-hydroxypropyl) -

ethanolamine

Dodecyl diethanolamine or

N- (3-dodecyloxy-2-hydroxypropyl) -

ethanolamine

Glycerin

Dodecyl diethanolamine or

> H 3-dodecyloxy- 2-hydroxypropyl) -

ethanolamine

Glycerine (a) monostearate surface resistance in ohms at 50% rel. Humidity and 23 ⁰ C and 1 day after production

> 10 ¹³

> 10 ¹³ 4 x 10 "x 10 ¹²

10 ⁿ

10 ¹¹ 7-10 ¹²

10 "

■ 10 ⁱⁿ

· 10 '° 10 "

10 ¹² > 10 ¹³

> 10 ¹³

10 ⁿ

Decay of the charge *)

Ash residue **) at 50% rel.

Humidity and 2.V C

very slowly

very slowly

slowly, slowly, slowly, slowly

very quickly

quickly

rel. quickly

very quickly

slow

very slowly

very slowly

slow

Remarks

0 sample

Comparative example

Comparative example

Comparative example

Comparative example

Comparative example

Comparative example

is claimed

is claimed

is claimed

is claimed

Comparative example

Comparative example

Comparison! example

Comparison: example

Continue Tune

example

Divide up

100 parts polymer

0.1 0.5

0.1

0.5 0.1

0.5

0.1 0.5

0.1 0.5

Recipe

Dodecyl diethanolamine or

N- (3-dodecyloxy-2-hydroxypropyl) -

ethanolamine

Glycerin O y! ™ "H. _Ie from stergemisch

80% a-Mor.ostearate and 20%

Glycerin

Dodecyl diethanolamine or N- (3-dodecyloxy-2-hydroxyprop> ¹ !) Ethanolamine

Glycerine-glycerine ester mixture of 80% fi-monolaural, 20% glycerine

Dodecyl diethanolamine or N- (3-dodecyloxy-2-hydroxypropyl) ethanolamine

Glycerine-glycerine ester mixture, consisting of 65% («+ /?) - monostearate, 15% distearate, 1% tristearal, 19% glycerin

Dodecyl diethanolamine or N- (3-dodecyloxy-2-hydroxypropyl) ethanolamine

Glycerine-glycerine ester mixture, consisting of 55% α-monostearate, 45% glycerine

Dodecyl diethanolamine or N- (3-dodecyloxy-2-hydroxypropyl) ethanolamine

Glycerine-glycerine ester mixture of 52% (α + / i) -monostearate, 34% distearate, 3% tristearate, 11% glycerine surface conflict in ohms
at 50% rel. Lufifcuchte and 2nd VC
and I day after
Manufacturing

U) ⁹

10 "

3-10 "

■ 10 ^i:

4- 10 "

10

Decay of the charge * ι

very
quickly

very
quickly

very
quickly

slow

slow

Ash test *) at

50% rel. I-uft-

damp and 2.VC

Remarks

is claimed

is claimed ι

is claimed

Comparative example

Comparative example

Tabel!! Polybutene injection molded parts! 1)

example Parts
on
lOO parts
polymer Recipe surfaces
resistance in ohms
at 50% relative air
humidity and 23 C
and 1 day after
Manufacturing Fade away
the on
charge*) Ash-
test **) at
50% rel.
air
damp
and 23 C Remark bad 1
2
3
4th
5 0
1.5
1.5
1.5
0.2
0.7 Polybutene (l)
(D = 0.915, r _lrcd = 4)
Glycerin
Glycerol (n) monostearate
Glycerine-glycerine ester mixture, be
consisting of 65% monostearate,
15% distearate, 1% tristearate,
19% glycerin
Dodecyl diethanolamine or
N- (3-dodecyloxy-2-hydroxypropyl) -
ethanolamine
Glycerin > 10 ¹³
> 10 ¹³
5-10 ¹²
5 10 "
> 10 ¹³ very
slow
very
slow
slow
quickly
very
slow (-)
+ 0 sample
Comparison;
example
Comparison!
example
will be bear
spoke
comparison
example

Parts 2 005 854 11th continuation Recipe surfaces I. 12th - ash Remarks on
IOO parts resistance in ohms Fade away
the on test * · I at polymer at 50% rel. Air
humidity and 23 ^: C charge*) 50% rel.
air Dodecyl diethanolamine or and 1 day after damp Comparison 0.2 N- (3-dodecyloxy-2-hydroxypropyl) - Manufacturing slow and 23 'C example example ethanolamine 5 ■ 10 ¹² (-) Glycerol (u) monostearate 0.7 Dodecyl diethanolamine or will bean 6th 0.2 N- (3-dodecyloxy-2-hydroxypropyl) - very says ethanolamine 10 ⁹ quickly + Glycerin-G lyccrincstergernisch, be 0.7 consisting of 80% a-monostearate, 7th 20% glycerin Dodecyl diethanolamine or will bean 0.2 N- (3-dodecyloxy-2-hydroxypropyl) - very says ethanolamine 10 ⁹ quickly + Glycerine-glycerine ester mixture, be 0.7 consisting of 65% monostearate, 8th 15% distearate, 1% tristearate, 19% glycerin Dodecyl diethanolamine or Comparison 0.2 N- (3-dodecyloxy-2-hydroxypropyl) - slow example ethanolamine 5 · 10 ¹² (-) Glycerine-glycerine ester mixture. be 0.7 standing from 35% ii-monostearal. 9 45% glycerin

Table III

Hollow bodies and films made of polyethylene (Examples 2 to 6 relate to hollow bodies and blown films; Example 7 - flat films)

example Parts
on
lOO parts
polymer Recipe surfaces
resistance in ohms
at 50% rel. air
humidity and 23 ° C
and 1 day after
Manufacturing Fade away
the on
charge*) ash
test **) at
50% rel.
air
damp
and 2VC Remarks 1 0 LP polyethylene
(D = 0.948. _{> Lrcd} = 2.4) > 10 ¹³ very
slow - O sample 2 1.5 Glycerin - («) - monolaurate 10 ¹² slow Comparison
example 3 1.5 Glycerin > 10 ¹³ very
slow - Comparative
example 4th 1.5 Glycerine-glycerine ester mixture, be
consisting of 85% σ-monolaurate,
15% glycerin 3 10 ' quickly + will bean
says 5 0.15
1.2 Dodecyl diethanolamine
Glycerine-glycerine ester mixture
according to example 4 110 ' very
quickly +
+ will bean
says 6th 0.15
1.2 N- (3-dodecyloxy-2-hydroxypropyl) -
ethanolamine
Glycerine-glycerine ester mixture according to
Example 18 of Table I. 2 10 ' very
quickly + will bean
says 7th 0.2
0.5 Dodecyl diethanolamine
Glycerine-glycerine ester mixture
according to example 4 2 10 ' very
quickly + will bean
says

Claims (2)

Patent claims: 1. Antistatic molding compositions for the production of molded articles from polyolefins, the Fcttsäureglyceride and contain glycerol, characterized in that these 0.2 to 2.8 percent by weight, based on the molding compound, of a mixture of a) 60 to 96 percent by weight of glycerol monoester of a fatty acid with 12 to 26 carbon atoms, the di- and triester content of which is at most 25 percent by weight of the glycerol-glycerol ester mixture, and b) contain 40 to 4 percent by weight glycerol. 2. Antistatic molding compositions according to claim 1, characterized in that 0.05 to 0.8 percent by weight of the mixture consisting of a) and b) through c) an alkoxylated amine of the formula R - (OCH ₂ -CHOH-CH ₂ ) _r -N