DE2166291A1 - ANTISTATIC EQUIPMENT OF PLASTIC MOLDED BODIES - Google Patents

Description

DipL-lng. P. WIRTH · Dr-Y-SCHMIED-KOWARZIK Dlpl.-lng. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

281134 'β FRANKFURT AM MAIN

TELEPHONE TO611> ■ '

287014 GR. ESCHENHEIMER STRASSE 39

Case 150-3182 / 1 . March 9, 1973

SK / Fri «.

S A IT D 0 Z AG GH-4002 Basel / Switzerland

¹¹ Antistatic treatment of plastic moldings "

(Ausseheidungsanmeldung from the application: P 21 32 805ο2-43 - Case 150-3182-)

It is known that many! Plastics such as polyolefins, polystyrene, synthetic polyamides or polyvinyl chloride as moldings, fibers or foils have the property of becoming electrostatic due to external influences charge, which leads to difficulties in processing and handling the plastics.

Numerous methods have been proposed in order to prevent or at least reduce this electrostatic charge been. For example, it is known that the surface of fiber bodies can be coated with antistatic agents to be changed in such a way that static electricity is prevented

309831/1039

The protection achieved in this way, however, only lasts until the applied layer through use the objects have been wiped off or loosened. However, lasting effects can only be achieved if the plastics are used Antistatic products are incorporated, which migrate slowly to the surface and for a long time Develop an antistatic effect For practical purposes, it is necessary that such an antistatic Means, used in small amounts, have a sufficient effect and the properties of the substrate not adversely affected. In particular, it should also have good heat stability and the decomposition- Do not accelerate the speed of the substrate at high temperatures.

It has now been found that the compounds described below can be incorporated into the plastics and give good antistatic effects. The invention relates to compounds of the formula

RC0KH (CH ₂ ) ₅ N- (CHg) ₅ -U (i)

R-CO- the acyl radical of 8 to 18 carbon atoms containing fatty acids,

R-j, Rp and R ~ are each independently hydrogen, or a residue of the formula

1-2 ^Me

where ρ = 1 or 2, Me is a mono- or divalent metal ion and at least one of the

Symbols _ "_

309831/1039

R ₁ , R ₂ , R ₅ for

Me stands.

These compounds are particularly suitable for antistatic finishing of polyolefins, polystyrene, synthetic Polyamides or polyvinyl chloride.

For the preparation of compounds of formula (I) goes one before that one mole of the compound of formula

R-CO-HH-COH ₂ ) ₃ ~ MH- (CH ₂ ) ₅ · -NH ₂ ^ ¹¹¹ ^

alkylated with 1 to [3 moles of haloalkylcarboxylic acid or an unsaturated carboxylic acid.

The haloalkylcarboxylic acid used is, for example, chlorine or Bromoacetic acid or ß-chloropropionic acid. One can also a low-molecular unsaturated acid, e.g. o £, ß-unsaturated carboxylic acid, e.g. acrylic, methaeryl or crotonic acid.

The compounds of the formula (HI) which are used can, for example, by reaction, for example at 130-24O ⁰ C, of 1 mol of dipropylenetriamine of the formula

H ₂ N- (CH ₂ ) ₃ -HH (CH ₂ ) ₅ -SH ₂ (II)

with about 1 mole, e.g. 0.9 to 1.2 moles, fatty acid of the formula R-COOH.

Carboxylic acids of the formula H-COOH are saturated or unsaturated, optionally branched but preferably straight-chain natural or synthetic fatty acids which contain at least 8, for example 9 to 17, preferably 9 to 11 carbon atoms.
For example:

309831/1039

216629T

Capric acid, lauric acid, myristic acid, palmitic acid, Stearic acid, coconut fatty acid, linoleic acid, oleic acid, tallow- « fatty acid, sperm oil fatty acid.

The sodium or potassium salts are preferably prepared Compounds of the formula (I), since these are particularly stable in storage are and give very good results when used »

309831/1039

The compounds of the formula (I) can be known per se Methods in which plastics are incorporated: for example, they can be immersed in a suitable solvent, e.g. Ethanol, trichlorethylene, toluene or eenzene, dissolve or disperse (suspend or emulsify) and then the Add polymer powder while stirring well, after which the Solvent can be removed e.g. by distillation,

or you can place them in the heat and optionally the thermoplastics Mix in under pressure and with thorough stirring, e.g. with a mechanical mixer. Man however, the incorporation of the antistatic agent into the polymer can also be carried out directly on the roller or e.g. Perform injection molding in an extruder. It is beneficial to use the amount specified for a given amount of plastic of the compounds of formula (I) first into a smaller one

M

Incorporate a lot of plastic and then this preparation Treat the remaining amount of plastic to use. It is also advantageous to use such concentrated preparations manufacture and store them ready for use, Here, too, the further mixing can take place both in the presence and in the absence of solvents.

309831/1039

The masses with an antistatic finish can be used, for example, by known methods, e.g. pressing, injection molding, spinning or Calenders are further processed. You can also use the usual additives, such as plasticizers, dyes, pigments, Contain lubricants or fillers.

The compounds of formula (i) have good antistatic properties Effect and are particularly temperature resistant. The finished plastics retain their antistatic protection for a long time and their original color and transparency and are not prone to exudation or sticking.

The compounds mentioned are advantageously added to the plastics in amounts of 0.01 to 5 tons, preferably 0.1 to 1 percent by weight.

The parts and percentages given in the following examples are parts and percentages by weight. The temperatures are given in degrees Celsius.

309831/1039

" 1 -

example 1

100 parts of lauric acid and 58.5 parts of dipropylenetriamine were condensed at 150-210 ° C. and then ^{alkylated with 58 parts of the sodium salt 1} of monoehloroacetic acid at 80 ° C. in the presence of sodium hydroxide.
Main product: - *

"CHgCOONa

CONH (CH ₂ ) ₃ NH (CH ₂ ) ₃ N <"

Example 2.

112 parts of lauric acid and 58 parts * 5 dipropylenediamine were condensed at 150-21O ⁰ C and then alkylated with 116..5 parts of the sodium salt of Monoehloressigsäure at 80 ° G in the presence of sodium hydroxide.
Main product:

Example 3

112 parts of lauric acid and 58.5 parts of dipropylene were condensed at 150-21O ⁰ C and then alkylated with yjh parts of the sodium salt of Monoehloressigsäure at 80 ° C in the presence of Natriumhydroxrd.
Main product.

C ₁ Η ^, ΟΟΝΗ (CH _p ), N (CH ₀ )

CH ₂ COONa

ORilÖJNAt INSPECTED 309831/1039

112 parts of lauric acid and 5B>J> dipropylenetriamine parts were condensed at 150-190 ⁰ C and then dissolved with 142 parts Moncchloressigsäure alkylated in 1,050 parts ΐβ #iger Kaliuuihydroxydlösung at 80 ⁰ C with subsequent distillation of the water.

Main product;

CH ₂ COOK CH CONH (CH) N (CH) N <^

CH ₂ COOK ^ ^CH 2 ^C00K

Example 5

1:41 parts of oleic acid with 57 parts of dipropylene vmrden at 15Q C-210 ^p condensed and subsequent alkylation with 65 parts of the sodium salt of monochloropropionic in the presence of sodium hydroxide at 80 ⁰ C.
Main product:

,, CHpCH COONa

CH _(CH2) CH: CH (CHgJ ₇ CONH (CHG), NH _(CH2) ^ C

Example 6 .

86 parts of capric acid and 65 parts of dipropylene were condensed at 150-210 ⁰ C and subsequently alkylated at 80 ° C with 126 parts of the sodium salt of monochloroacetic acid in the presence of sodium hydroxide ·.
Main product:

CH ₂ COONa

), NH (CHp), N <^
_ * * ^ CH ₂ COONa

3 09831/1039 originally inspected

ff

Example 7

OeIsäure parts and 57 parts Diprpylcntriarnin were condensed at 150-210 ⁰ C and connect: .d .with 58 parts of the sodium salt of föoncchloressigsäure in the presence of sodium hydroxide at 80 ° C is alkylated.
Main product:

CH ₅ (CHg) _? CH: CH (CHg) C ONH (CHg) NH (CH ₃ ) ^

^ CHgCOONa

309831/1039

Claims (3)

Claims 1. Compounds of the formula RCONH (CHp) = N- (C) O = ΝΓ. (I) in which. R-CO- denotes the acyl radical with 8 to 18 carbon atoms holding fetal acid, and R _v each independently of one another hydrogen, or a radical of the formula - (CHp-) COOL ₂ Me v / orin ρ = 1 or 2, and Me a one or 2-valent metal ion mean and at least one of the symbols R _n . R ₀ ' ^R -4 ^{stands for} ^ CH) -COÖ] Me. it!} L ^P J 1-2 2. Process for the preparation of the compounds according to claim 1 j characterized in that 1 KoI of the Ver binding the formula R-CO-NH- (CH ₂ ^ NH- (CH ₂ ) - NH ₂ (III) alkylated with 1 to 3 moles of Haiogenalkylcarboxylic acid or an unsaturated carboxylic acid. 309831/1 & 39 ^{8AD 0RleiNAI} - Compound of formula C, H ₀ -XOMH (CH ₉ ), NH (CH ₀ ), NHCH ₀ CODHa 4 ·. Compound of formula C ₁ -, H ₀ ^ CONH (CH ₀ ), NH (CH ₀ ). CH ₂ COONa 5 · Compound of Formula H ₂ COONa CH ₂ COONa 6. Compound of Formula CH COOK) -N- (CH) N CH ₂ COOK 7 ". Compound of the formula C ₁ "H" CONH (CH_) -, - NH- (CH ₀ ), NHCK ₀ COONa β. Compound of formula C, "H, _V CONH (CH ₀ ), NH (CH ₀ ), NHCH ₀ CH ₀ COOMa ORIQIWAL INSPECTED 309831/1039 9 · Compound of Formula CH CONH (CH) NII (CH). SANDOZ A.G. 3098 31/1039 Subject: File number P 21 32 805.2-43 German patent application Case 150-3182 Comparative experiments Process description Of the antistatic agents A / B, C, D, E and F mentioned below, compounds A, B, D and E were incorporated into polyethylene and polypropylene in a concentration of 0.1 and 0.5 percent by weight, respectively, by means of a roller mill. The plates obtained were then stored at 50% relative humidity for 14 days at 23 ° C. The antistatic agents C and F were incorporated in polyvinyl chloride at a concentration of 1% and the air conditioning was carried out for 48 hours at 65% relative humidity and 20 ^° C. The surface resistance and half-life of the samples were measured in accordance with DIN 53 482. The polyethylene used was made in a low-pressure process. Density 0.957 g / cm (Hostalen GC 9630). 3 The polypropylene had a density of 0.908 g / cm (Carlona PM 61). The polyvinyl chloride had a density of 1.39 g / cm (Ha- loric hard polyvinyl chloride PEB 911).
ν 309831/1039 -X- As products from the present application file number P 21 32 805.2-43 were chosen: Product A: C ₉ H ₁₉ CONH (CH ₂ ) ₃ NH (CH ₂ ) NH ₃ , Product B: C ₁₁ H ₂₃ CONH (CH ₂ J ₃ NH (CH ₂ ) NH ₃ and. Product C: C H CONH (CH) NH (CHJ J .CH ₉ COONa COONa As comparison substances, the product D: CH, (CH ₀ ) ^ -CH-NH-C-CH., 3 2 16 2 Il 3 according to DOS 1.494.052, table 1, example 2 Products : N-CH ₃ -C NH (CH ₂ ) ₂ O-C according to DAS 1.215.151, example 1 Commercial product Gafstat RS 710 (General Aniline) = product F 309831/1039 - 2? - · 1S 2166791 Compilation of the results polymer Additive surfaces
resistance
(in ohms) . Half-life
(lake.) Polyethylene Product A. 5-1O ¹¹ 15-60 Il B. 3-10 ¹⁰ 1 Il ¹¹ D 4-10 ¹² > 60 Il ¹¹ E. 6.1O ¹² > 60 polymer Additive surfaces
resistance
(in ohms) Half-life
(lake.) Polypropylene Product A. 4.1O ¹¹ 4-10 Il B. 3-1O ¹¹ 2-4 Il ' ⁿ D 4-10 ¹² > 60 II "E. 5-10 ¹² > 60 polymer Additive surfaces 10 Half-life resistance (lake.) (in ohms) Polyvinyl chloride Product C 10 ⁹ <1 10 Il η ρ 2-3 30983 1/1039 2166791 It is clearly shown that the products according to the invention A, B and C the prior art products D, E and F are superior in antistatic properties. 309831/1039