DE2153438A1 - ANTI-ELECTOSTATIC MOLDS AND SHAPED BODIES - Google Patents

Description

Anti- static. Molding compounds and .. "Shaped bodies (addendum to patent application P 20 05 854.2)

The invention relates to 'a further development of the anti-electrostatic Molding compositions and moldings made from polyolefins, the Fatty acid glycerides. and contain glycerine, according to patent application P 20 05 854.2.

US Pat. No. 2,758,984 and DT-AS 1,271,391 disclose mixtures from polyethylene on the one hand and from polyhydric alcohols or fatty acid glycerides in the presence of adsorbers, as well on the other hand known from glycerine-free mono- and diglycerides. It is also known for antistatic equipment to use of polyolefins fatty alkyl dialkanolamines, both on their own (US Pat. No. 2,992,399) and in Combination with other antistatic compounds (DT-AS 1 230 210 and 1 234 020).

The use of polyhydric alcohols like glycerin is in view to an antistatic effect, as will be shown, completely unsatisfactory. On the other hand, glycerol esters behave very different.

DT-OS 1 927 677 teaches that the monoglycerides are more saturated C-. 2 ~ to C-, "-fatty acids can be used as antistatic agents, but do not have a noticeably good effect. Particularly effective Monoglycerides should be Cg to C, fatty acids and possibly

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contains little glycerine. For this reason, too a process for the production of the purest monoglycerides is given. 'I.

It is the subject of the parent application P 20 05 854.2, and it is known from the equivalent BE-PS 762 713 that when the monoglycerides are used, the C _,? ~ to C _? The anti-static effectiveness of fatty acids increases when they are replaced by up to 40 %, preferably 10 to 30% by weight, with glycerine, with 25% for polypropylene, 20% for polybutene and 15% by weight for polyethylene.

It was therefore very surprising to find that in the case of polyethylene a further replacement of the monoglycerides by glycerine above 40 percent by weight, the decrease in the anti-electrostatic observed in the range of this concentration The effectiveness of the mixture is replaced by a new range of high effectiveness, even the first, already described still surpasses; and this, although the inherently more effective component, the monoglyceride, to a much lesser extent Percentage than is included there.

The object of finding even more effective and even more inexpensive additional mixtures is achieved according to the invention through a mixture of

a) 20 to less than 60 percent by weight of glycerol monoester a fatty acid with 12 to 26 raw material atoms, whose Content of di- and tri-esters at most 25 percent by weight the glycerine-glycerine monoester mixture is and

b) more than 40 to 80 percent by weight of glycerol, based in each case on the glycerine-glycerine monoester mixture,

containing polyethylene.

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The .Mixtures preferably consist of 30 to. 55 percent by weight of component a, wherein the fatty acid is preferably 12 to 18, in particular 14 carbon atoms, and from 45 up to 70 percent by weight of component b,

■ "A sufficient effect is achieved if the polyethylene ■ molding compositions and molded bodies have a content of 0.2 to 2.8 percent by weight possess the mixture of cv and b. .

5 to 25 percent by weight of the mixture consisting of a and b can according to a particular embodiment of the Invention by,.

c) an alkoxylated amine of the formula - ,. '..

R- (OCH ;, - CH - CIL) ₁ . - N

R ₀

be replaced, where R is an alkyl or alkenyl radical with 6 to 26 carbon atoms, R ₁ and R ₀ the radical (CH ₀ 0) H with χ = 2 or 3 and η = '1 to 5; R ₀ also denotes hydrogen, X = H or OH and z = 0 or 1.

All high and low pressure polymers are suitable for finishing of ethylene, especially those with '/, values from 0.4 to 4.0, corresponding to average molecular weights from 20,000 to 200,000, as well as copolymers of ethylene and polymer mixtures with polyethylene. The new additives can preferably be used on Ziegler low-pressure polyethylene, especially one such as can be achieved with the help of titanium compounds such as titanium tetrachloride or clilortitanic acid alkyl esters on the one hand and of / aluminum compounds such as alkyl aluminum chlorides and sesquichlorides on the other hand.

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The antistatic glycerine-glycerine ester combination (components a and b) is obtained either by glycerolysis of fats and oils or by esterification of glycerine with fatty acids. For example, heated fatty acids in an approximately 7- to 8-fold molar excess of glycerol to about 200 to 220 ⁰ C (Hundeshagen, J.pr. (2-), 2JB, 225) or sets the lld.- or K Salts such fatty acids with a cC- or ß-ealogenpropylene glycol (see, for example, Guthe, eg 44, 83) and finally add the required amount of glycerine in each case. The following fatty acid components may be mentioned as useful fatty acid components: 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 cC- or ß- or (<£ + ß) -glycerides: ß- Monoarachin, ß-monobehenate, o ^ -lignocerin, especially o (-monostearin, ß-monostearin, (cC + ß) -monostearin, <j [-monopalmitin, {° ifr ß) -monopalmitin, cC-monomyristin, eC-iyönoolein, «+ Ss) -monoolein, as well as mixtures of these like / fcC- or ß or (o & l · ßJ _ / - ^ mono3tearin / monopalmitin or ^ + ß or (cG + ßl / -monostearin / monoolein or ^ / or. Ss or (? C + ßJ _ / - monopalmitin / monostearin / monoolein or £ pC or ß or (eO + ß2 / -monolaurin / monomyristin. ■

Suitable alkoxylated amines of the formula

■ -. z ¹

R - (OCH ₉ - CH - CH ₀ ), - N

X ^R 2

(Component c) are, for example, hexacosylaminomonoethylene glycol, nonadecyl-N- (ß-oxäthyl) -amino diethylene glycol , hexadecylamino- · tetraethylene glycol, decylaminoheptaethylene glycol, undecen- (10) -yl-propylene-hydroxyl-2-hydroxypropylene (3-hydroxypropylene) glycol, N- -KT-ätlianolamine, N- (3-nonadecyloxy-2-hydroxypropyl) -N-diethanolamine and especially dodecyldiethanolamine, tridecyldiethanolamine, pentadecylmono- or diethanolamine, heptadecylmono- or diethanolamine, octadecyldiethanol-

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amine _# N- (S-dodecyloxy ^ -hydroxypropyl) -mbno-ethanolarain, N- (3-ItodecyloJ3f-2-hyäroxypropyl) -diethanolamine, N-hexylaminotetradecylethylene glycol, dodecyloxypropyldiethanolamine, hexadecyloxypropyldiethanolamine, hexadecyloxypropyldiethanolamine can also be used.

The mixtures of a, b and possibly c can be on the one hand the surfaces of the moldings (e.g. by dipping or spraying, if desired, in water or organic solvents dissolved mixtures), on the other hand work into the polyethylene. (The component c) is thereby in an amount of 0.05 to 0.7, preferably 0.1 to 0.4 percent by weight used.

The antistatic substances can be incorporated, for example, into the polymer in powder form with the aid of a simple mixer. The mixture obtained can then be fed to the processing machines ^{either directly or after previous compression to give granules and shaped here in the temperature range of 120 to 300 ° C. applicable to the polymer.} In order to achieve good and rapid distribution, it is sometimes advantageous to introduce the antistatic compounds in dissolved form. The antistatic agent can also be incorporated into the polymer directly on the roller or, for example, during injection molding in an extruder.

The method of initially using an antistatic agent has also proven itself highly concentrated granules, and this during processing by adding additive-free granules to the ■ to bring the desired antistatic content.

You can use additional ones that are otherwise common in plastics processing Add additives, e.g. dyes, stabilizers, plasticizers, Extenders and fillers, as well as lubricants.

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Usual stabilizers are phenolic antioxidants, such as 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 useful to add substances to the polymers add the slight yellowing of the amine component that occurs after prolonged exposure to high temperatures impede. Suitable stabilizers of this type are, for example, phosphorous acid esters, in particular didecylphenyl phosphite, Decyldiphenyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, Tris- (nony! Phenol + 9 mol ethylene oxide) phosphite, which are added in amounts of 0.01 to 0.4 percent by weight, based on the polyethylene. Also works an addition of alkanesulfonates, e.g. pentadecanesulfon- acidic sodium, in the same way beneficial. This requires about 0.01 to 0.4 percent by weight, based on the Polymers.

These additives usually do not affect the antistatic effect. If this is due to a very high filler content of chalk, fiberglass, asbestos etc. should sometimes still be the case, a slightly higher dosage creates Anti-static additives easily and quickly remedy.

The anti-static effectiveness of the additives is in the the following examples determined by measuring the surface resistance.

A low pressure polyethylene is used as the polyethylene

who turns it.

the density D = 0.960 and the melt index I ₅ = 18 to 20

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Like Examples 1 to 20, recognizable special in the graphic Representation, show, the mixtures of glycerol monoester of a fatty acid with glycerol are best, the more than 40 to 80 percent by weight glycerin (Examples 7 to 11, 13, 14 and 17), especially those that are 45 to 70 percent by weight Contain glycerine (Examples 7 / to 10, 13, 14 and 17), compared to the mixtures with 40 and 10 percent by weight glycerol (Comparative Examples 6 and 12). When comparing the Mixtures according to the invention with the pure glycerol (No. 1) and the pure monoglyceride (No. 2) is the considerable advance of the claimed molding compounds can be seen. Like example 18 to 20 show that the addition of a compound of type c) increases the effect of the mixtures a) + b).

If the polyethylene used is replaced by one that has a density D - 0.948, a reduced viscosity f / , = 2.4 and a melt index I ₅ = 1.0 to 1.3, comparable results are obtained.

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Tabel

Example-
No. Weight part
le to 100 Ge
important steep
polymer additions surfaces
resistance
/ M O / be i
29-23 ^° C Days after
the her
position
d. test specimen. relative air
damp
/ 3U- Remark
gene 1 0 to 2.8 Glycerin 1 to 20 40 and 60 Comp. Ex 2 2 S tear in s äu remonogIy-
cerid 9-10 ⁵ 1 40 Il O 3
4th 1.5
1.2 1-10 ⁶
1-8-1O ⁶
1 · 4 · 1Ο ⁶ 1
1
8th 40
40
40 Il
Il
It 98 18 / 5 1 * 0 5-1Ο ⁶ 1 40 Il - * 6th 2 Mixture of 60 %
Stearic acid mono-
glyceride and 40 %
Glycerin 9 1Ο ⁵
4 · 10 ⁵
4 · 10 ⁵ 1
1
8th 40
60
40 "(see fig.)
Il 1 «
Il Il 00 5 · 1Ο ⁵ 8th 60 Il Il 7th 2 Mixture of 55 %
Stearic acid mono-
glyceride and 45 %
Glycerin 5.10 ⁴
1-4-10 ⁴
3-6-1O ⁴ 1
1
8th 40
60
40 see fig.
H
Il 1-10 ⁴ 8th 60 Il 8th 2 Mixture of 50 %
Stearic acid mono-
qlyceride and 50 % 2 · 10 ⁴
5 * 10 ³
. 1-4-10 ⁴ 1
1
8th 40
60
40 Il
Il
Il

Glycerin

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3 * ΙΟ ³ 8 60

Mixture of 40% stea- 2 x 6 x 10-1 ric acid monoglyceride and 4 * 5 x 10 ^ 7 1 60% glycerol 2-4 x 10.8

2 Gordian made of 30% stearin- 8 * 10 . 1

acid monoglyceride and 2-4 * 10 1

70% glycerine 6.10 . 8th

1-8- \ QT 8

**> 11 2 Camisch made of 20% stearin- 3 * 10, - 1

* ■? acid monoglyceride and 6 * 10 _fi 1

II 80% glycerin 5-5-10 8

_> 1-10? 8th co 12 2 mixture of 10% stearin-P "1O 1 and 8 40 * -> acid monoglyceride and

- »■ 90% glycerine 3 -

- * 13 2 Mixture of 50% laurine- 9 "1 ° 3 1

~ * acid monoglyceride and \ '\ 0. 1

50% glycerin 1 x 10.8

l-iof 8

2 mixture of 50% myristic-7 "10, 1

acid monoglyceride and ^ * 1 ° 3 ■ *.

50% glycerine 8 x 1θ, 8

1.1Q3 8

ft. i: o ⁵ frig «ί

17 2 mixture of 42% myristic 8.10 ³ "1 40

acid monoglyceride, 7% diglyceride, -? 1% trigly- _ </ i

ceride and 50% glycerine 1 * 10 1 60 <jJ

40 Il 60 ■ I 40 M. 60 Il 40 Il 60 Il 40 " 60 Il 40 Il 60 Il 40 Il 60 ii and 60 Comp. Ex. (see illustration) 40 60 40 60 40 60 40 60 40 40

18th 0.15
1.0 19th 0.15 ok 20th 0-15

1.0

- 10 -

Dodecyl diethanolamine 2 · 10 ₉ mixture according to Example 14 9-10

Dodecyloxypropyldiätha- ₃ ethanolamine 1-1O ₉

Mixture according to example 14 8 * 10 "

Κ- (3 ~ bodecyloxy-24rydroxy ~ 5 · 10 "prppyl) -ethanoiamine ' ₃

Mixture according to Example 14 2-10 O.Z. 2591

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60 1
1 40
60 1
1 40 1 60 1

Claims (3)

Claims b) more than 40 to 80 percent by weight of glycerine, respectively on the glycerine-glycerine monoester mixture, containing polyethylene. 2. Antistatic molding compositions and moldings according to claims 1 and 2,
marked by a content of 0.2 to 2.8 percent by weight, based on the molding compositions, of the mixture of a and b. 3. Antistatic molding compounds and moldings according to Pa- ■ ' claim 1 and 2, characterized in that 5 to 25 percent by weight of the mixture consisting of a and b by c) an alkoxylated amine of the formula ¹ R - (OCH ₀ - CH - CH-J - N Z , Δ Z \ x ' ^R 2 are replaced in which R is an alkyl or alkenyl radical with 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 5, R ₂ also V hydrogen, X = Hydrogen or hydroxyl and ζ = 0 or 1 mean. 09818/1118 Blank page