DE2437771C3 - Internal antistatic for polyamide - Google Patents

Description

wherein

R is a straight-chain or branched alkyl or alkenyl radical with 8-24 carbon atoms,

η 2 to 6
and

X Ibis 5

mean and the sum of p, q and r in the molecule on average occurring ethyleneoxy groups is 40 to 150, as an antistatic component.

2. Inner antistatic for polyamide according to claim 1, characterized in that it is as Compounds of the formula (I) those of the formula

(CH ₂ CH ₂ Or ,, Ή
RN 'CH, CH, CH, N

wherein

R Ci4-22-alkyl
and

ρ + q + r 45 to 60
mean contains.

(CH ₂ CHjO) ₁ , -H

(ClWM ₂ Ot -Il

(II)

It is known from US patent specification 28 09 159, synthetic fiber material such as polyamide, polyester or polyacrylonitrile due to the external application to impart antistatic properties to certain alkylolamines. However, these equipments have the disadvantage that the permanence is usually insufficient, and that the use of other aids is necessary is. Another attempt to make antistatic fibers has been to use an antistatic material Add polymer before shaping. However, external antistatic agents cannot do this without further ado be used because of the diffusion and migration processes of the antistatic agents in the substrate Conditions must be set.

So that the antistatic agents can withstand the usual higher temperatures when the plastics are deformed can, their chemical stability should also be sufficiently high. It should be used during and after the deformation no undesired conversion of the antistatic agent with the plastic takes place.

Likewise, the mechanical properties of the plastic should not be affected by the presence of the Antistatic are adversely affected. For the internal processing different Antistatic agents such as polyethylated fatty alcohols or fatty acids according to DE-OS 21 09 030 are used.

However, these products must be so high in order to have a sufficient antistatic effect Amounts are used that the mechanical properties of the fiber are adversely affected.

The use of various alkoxylated amines as internal antistatic agents for plastics is in the US Patent 36 57 386 and in German Offenlegungsschriften 19 23 066, 2158 552 and 22 51 280.

The internal antistatic agents according to US Pat. No. 3,657,386 are tetrols which, due to the manufacturing process, are have a relatively symmetrical structure. Also the internal antistatic agents described in DE-OS 19 23 066 are tetrols or tetroid derivatives with a relatively symmetrical structure.

The internal antistatic agents described in DE-OS 21 58 552 are alkoxylation products of fatty alkyl monoamines with a relatively low degree of alkoxylation. The inner described in DE-OS 22 51280 Antistatic agents are ethoxylation products of propoxylated mono- or polyamines, whereby the degree of alkoxylation is relatively high, especially in the case of the polyamines. These internal antistatic agents show in Polyamide has a measurable antistatic effect; but it was surprisingly found that Particularly good internal antistatic agents for polyamide are those in which the antistatic active substance of the equates to formula (1) below.

There are other alkoxylation products in the literature described by amines, so z. B. in US Patent 35 41 041 in BE-PS 7 41 324 and in NL-PS 2 96 004; a usability of the compounds mentioned there as internal antistatic agents for However, polyamide cannot be found in the last three patents mentioned.

The invention relates to an internal antistatic for polyamide, characterized by a content of one or more tertiary amines of the average formula

(CH ₂ CH ₂ OL; -H

-N

(CH ₁ CH ₁ Qh-H

(D

a straight-chain or branched alkyl or alkenyl radical with 8 - 24 carbon atoms,
2 to 6,

χ Ibis 5

and the sum of p, q and r occurring on average in the molecule ethyleneoxy groups is 40 to 150, as an antistatic component.

The tertiary amines of the formula (I) or mixtures thereof, which according to the invention are used as internal antistatic agents are used for polyamidine material and which correspond to the preceding structural formula are those, which have a straight-chain or branched alkyl or alkenyl radical with 8-24 carbon atoms and are derived, for example, from the following amines:

N-aminopropylcocosylamine,

N-Aminoäthylmyristylamin,

N aminopropyl myristylamine,

N-aminobutyl myristylamine,

N-aminopentyl myristylaniine,

N-aminohexyl myristylamine,

N-aminoethyloleylamine,

N-aminopropyloleylamine,

N-aminoethylbehenylaniin,

N-aminopropylbchenylaniine,

N-aminobutylbehenylamine,

N-aminoethylarachinylamine,

N-aminopropylarachinylamine,

N-aminobutylarachinylamine,

N-aminoethyl tallowamine,

N-aminopropyl tallowamine,

N-cocosyldipropylenetriamine,

N-stearyl-diethylenetriamine,

N-stearyl-dipropylenetriamine,

N-stearyl-triethylenetetraamine,

N-stearyl-pentaethylene hexaamine, N-myristyl dipropylenetriamine,

N-myristylhexaniethylenediamine, N-palmityl diethylenetriamine,

N-palmityl-dipropylenetriamine, N-oleyl-dipropylenetriamine,

N-behenyl-dipropylcn-triamine, N-arachinyl-diethylenetriamine,

N-lignoceryl diethylenetriamine,
N-tallow dipropyleni riamin,
N-tallow-triethylenetetraamine,
N-tallow tetraethylene pentaamine,
"> N-sebum tripropylenetetraamine,
and / or their mixtures.

The sebum and coconut residues are derived from the sebum and coconut fatty acid gels, which are derived from natural sebum and

ι »Coconut fats are made derived. The tallow fatty acid mixture consists mainly of the saturated acids such as lauric acid (Cu), myristic acid (Cm), palmitic acid (Ck,), stearic acid (C | _B ), arachidic acid (Qo); the monounsaturated acid, e.g. B. Oleic Acid (Cm)

ι ") and the diunsaturated acids, e.g. linoleic acid (C ₁₈ ).

The coconut fatty acid mixture mainly contains saturated acids such as capric acid, lauric acid, myristic acid, Palmitic acid, stearic acid and unsaturated

2Ite acids such as oleic acid and linoleic acid.

Amines with alkyl and alkenyl radicals of chain length Cu to Ci ₈ , which are derived from acid mixtures that are produced from soybean oil, are also suitable: such acid mixtures mainly consist

2> from palmitic acid, stearic acid, oleic acid and linoleic acid.

The tertiary amines of the formula (I) or their

Mixtures can be prepared in a manner known per se by the fact that the starting amines or their mixtures with the desired amount of ethylene

iii oxide reacts under oxyalkylation conditions.

The tertiary amines or their amines are used for the internal antistatic treatment of the polyamide material Mixtures expediently in linear, synthetic, fiber-forming polyamides, d. H. Polymers that are essentially

j> chen the repetitive, through at least 2 Carbon atoms separate units

I!

- CNH-

have incorporated. The polyamides are known to those skilled in the art, and generally are formed by using essentially equimolar amounts of, for example, diamines and dicarboxylic acids

• π or different amino acids or combinations the same implements. Typical examples of such polyamides include polyhexamethylene adipamide and Polycaprolactam. The polyamide fibers can, in addition to the tertiary amine, matting, antioxidant

Ίο tion and whitening agents, viscosity stabilizers and plasticizers.

For an antistatic finish, it is possible to mix the tertiary amine with the polyamide before this is pressed into shapes or into threads

■) ■> extruded. Preferably 0.5 to 15 percent by weight, in particular 2 to 6 percent by weight of the internal antistatic, based on the polyamide, is then added.
It is also possible to use the tertiary amine

add the pre-condensate of the polyamide and afterwards to carry out the polycondensation.

The antistatic agent is preferably added to the monomer or monomers and the monomer or monomers then subjected to polycondensation. In

tv) d ^; In this case, preferably 1 to 8 percent by weight, in particular 2 to 6 percent by weight of the antistatic, based on the weight of the monomer, is added.

An antistatic agent composed of one or more compounds of the formula (1) in which R is an alkyl radical of chain length Ch to C. ₂ is preferably used.

An antistatic agent composed of one or more compounds of the formula (I) in which χ is 1 is also preferred.

An antistatic agent composed of one or more compounds of the formula (I) in which η is 3 is also preferred.

The sum of p, q and r in the compounds of formula (I) occurring on average ethyleneoxy groups is preferably 45 to 60.

Compounds of the formula are particularly preferred

R-- NCH, CH, (Ή, Ν

(CH ₂ C ^- H ₂ - Ot, H.

(CH ₂ CH ₂ - O) ₁ . H

wherein

R is an alkyl radical of chain length Cu to Cj;

ρ + q + r45 to 60

mean.

The finished polyamide has excellent antistatic properties even at relatively low levels of humidity Properties that are retained after repeated washing or cleaning. It has also been shown that the antistatic is present in the finished fiber material in a very fine, evenly distributed form and too does not result in agglomeration of, for example, added titanium dioxide. The mechanical properties of the Fibers are not adversely affected. In addition, they can be equipped with antistatic properties Fabrics made from fiber material show a reduced susceptibility to dirt and the Fibers containing antistatic agents are soft to the touch. The dyeability of the yarn or fabric is not or only insignificantly influenced.

The following examples serve to further illustrate the invention. The parts mean parts by weight, the degrees Celsius, and the percentages percentages by weight.

example 1

A reactor equipped with a heater and stirrer is charged with a mixture of 1520 parts ε-CaproIactam and 80 parts of aminocaproic acid and 64 parts of an antistatic agent, consisting of a mixture of several compounds of the formula

(CH ₂ CH ₂ O) (H (CH ₂ CH ₂ O) ₁₁₁ H

RN CH ₂ CH ₂ CH ₂ N

₂ CH ₂ CH ₂

(CH ₂ CHjO) ₁₁ H.

R to 1.3% a Ci ₄ H ₂ H-,
4.7% a CibHn,
42.0% a CnH) ₇ -,
to 12.0% a C ₂₀ H ₄ , -
and 40% a C >> Hr, -alkyl radical

means, and

/ + m + η = 50,

loaded. Then the mixture is purged with nitrogen and over one hour at atmospheric pressure heated with stirring to 255''C to initiate the polymerization. After another 4 seconds, heat under The polycondensation is ended by stirring and passing nitrogen through. Then the polymer is in the mold a tape extruded from the reactor. This is cooled, peeled, washed and dried.

The polycapronamide pellets containing the antistatic agent are melted at about 275 ° C., and the melt is ^{spun under a pressure of 105 kg / cm 2} through a 16-hole spinning plate with hole diameters of 0.35 mm to form a bundle of threads of 250 denier. The thread bundle is taken up at a speed of 305 m / min and drawn in a ratio of 1: 3.5, so that a yarn of 70 denier is obtained. A comparison yarn without an antistatic agent is produced in the same way.

If the humidity is 30 percent, after 10 washes at 60'C for 30 minutes with a Washing liquor that contains 5 g / l of a fully synthetic detergent has a better antistatic effect and a lower soiling behavior of the anti-antibiotic Polyamide-6 fibers can be observed.

Example 2

150 parts of hexamethylene diammonium adipate are placed in a high pressure stainless steel autoclave. 50 Parts of water and 4.5 parts of an antistatic agent, consisting of a mixture of several compounds π of the formula

(CH ₂ CH ₂ O) (H (C ^- H ₂ CH ₂ Oi ₁ JI

RN CH ₂ CH ₂ CII ₂ N

(CH ₂ CII ₂ Oi ₁₁ II

R to 1.3% a Ci ₄ H ₂ H-,
4.7% a CihH π-,
42.0% a CiKHi ₇ -,
12.0% a C10H41-
and 40% a C ₂₂ H ₄₎ -alkyl resol

■ »ι means, and

I + in + η = 110.

brought in. The autoclave is purged free of oxygen using purified nitrogen and the

ϊ5 temperature and the pressure slowly increased to 243 ⁰ C and 17.5 atü. During this time, steam is continuously released as the condensate. The inert pressure is then released to atmospheric pressure for approx. 25 minutes and the polycondensate is spun into yarn through a spinneret.

w) nen, with a deduction ratio of 4.7: 1 is stretched. Fabrics for the tests are made from the yarn.

At 30% humidity, after 10 washes at 60 C for 30 minutes with a

tv-. Washing liquor that contains 5 g / l of a fully synthetic detergent has a better antistatic effect and a Lower soiling behavior of the antistatic containing fibers made of Polvamid-66 can be observed.

Example 3

Fabric swatches are prepared as described in Example 1, except that instead of there Tertiary amine mixture used 96 parts, based on the weight of the polyamide, of a mixture tertiary amines of the formula

(CH ₂ CH ₂ O) J) (CH ₂ CH ₂ O) ₁ H (CH ₂ CH ₂ O) Jl

RN - CH ₂ CH ₂ -NCH ₂ CH ₂ -N

(CH ₂ CH ₂ O) ₁₁ H.

wherein
R.

Alkyl and alkenyl radicals with a chain length of C ₈ to Ci8, made from the acids found in coconut oil,

mean and

k + I + m + η = 90,

be used.

At 30% humidity, after 10 washes at 60 "C for 30 minutes with a Washing liquor that contains 5 g / l of a fully synthetic detergent has a better antistatic effect Antistatic containing fibers made of polyamide-6 can be observed.

Example 4

The procedure is as described in Examples 1-3, but the addition product is used as the internal antistatic agent of 100 moles of ethylene oxide to 1 mole of amine of the formula

C ₂₂ H ₄₅ -NH-CH ₂ -CH ₂ -CH ₂ -NH ₂

Example 5

The procedure is as described in Examples 1-3, but the addition product is used as the internal antistatic agent of 150 moles of ethylene oxide to 1 mole of amine of the formula

C ₂₂ H ₄₅ -NH-CH ₂ -CH ₂ -CH ₂ -NH ₂ .

Comparative experiments

Polyamide was made by polycondensing e-caprolactam and aminocaproic acid in the presence of 3% (weight) antistatic agent, analogous to Example 1 of the present patent application described, antistatic finish. The antistatic effect was assessed by measuring the half-life of discharge (half-life).

The following antistatic agents were compared:

1. The compound from Example 7 of the US patent 36 57 386 from

1 mole of H ₂ N-CH ₂ -CH ₂ -NH ₂

+ 35 moles C ₃ H ₆ O + 30 moles C ₂ H ₄ O

(which also falls under the definition of the compounds in DE-OS 19 23 066).

2. The connection analogous to Example 1 of DE-OS

21 58 552 from

1 MoIC ₁₂ H ₂₅ -NH ₂ + 20MoI C ₂ H ₄ O
(Average).

3. The compounds used according to the invention from

a) I mole of C ₂₂ H ₄₅ -NH-CH ₂ CH ₂ CH ₂ -NH ₂
+ 100 moles of C ₂ H ₄ O

b) 1 mole of C ₂₂ H ₄₅ -NH-CH ₂ CH ₂ CH ₂ -NH ₂
-I- 150MoI C ₂ H ₄ O.

4. The connection analogous to Example 25 of DE-OS

22 51 280 from

1 mole of C ₂₂ H ₄₅ -NH-CH ₂ CH ₂ CH ₂ -NH ₂
+ 100 moles of C ₃ HeO + 88 moles of C ₂ H ₄ O.

5. The connection from BE-PS 7 41 324 from
1 mole of C _la H ₃ 7-NH-CH ₂ CH ₂ CH ₂ -NH ₂
+ 10 moles of C ₂ H ₄ O

and

6. The connection from US Pat. No. 28 09 159 the end

1 mole of C ₂₂ H ₄₅ -NH-CH ₂ CH ₂ CH ₂ -NH ₂
^r> + 3 moles C ₂ H ₄ O.

The half-lives obtained in seconds at 25% relative humidity and the foam behavior at condensation are shown in the following table:

Antistatic agent HWZ (in seconds) Foam 4) 1) 60 0 2) 73 0 3 a) 6-10 0 3 b) 7-9 + 4) 15th 0 so 5) no measurement ++ 6) 120 +

Compound 5) foamed so much during the condensation that no usable polyamide was produced could be and therefore no measurement was possible.

Claims (1)

Patent claims: 1. Inner antistatic for polyamide, characterized by a content of one or several tertiary alines of the average formula (CH ₂ -CH ₂ -Oh-H R-hN - fCH, t 1 - _N (CH, -CH, -Ο) -, - H |. _v (CH, -CH, -O) - _r --H