DE2259104A1 - ANTISTATIC POLYAMIDE COMPOUNDS - Google Patents

Description

Bayer Aktiengesellschaft 2259104

Central area of patents, trademarks and licenses

509 Leverkusen, Bayerwerk Ad / Ku

^r i DEC, 1972

Antistatic polyamide compounds

The invention relates to polyamide compositions made from high molecular weight, linear, aliphatic polyamides with reduced surface resistance, by melt condensation of salts from aliphatic diamines and aliphatic dicarboxylic acids and / or are produced from lactams which contain polyester amides in a homogeneous distribution, which are formed by condensation of dicarboxylic acids or their derivatives, diols and primary-secondary aliphatic diamines.

Shaped structures such as foils, fibers and plates made of polyamides are known to have the property of themselves because of their electrostatically charge extremely high surface resistance during use. Especially when the outside temperature is low This occurs in heated rooms due to the low humidity on floors and carpets made of synthetic Polymers in the form of electric shocks are uncomfortable in appearance. But also in the technical area the use of plastics due to electrostatic discharge due to the increased pollution caused by the attraction of dust and fire hazard when handling flammable solvents

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highly limited.

225910A

A number of chemical compounds are known, which can be applied to the surface or incorporated in the polymer, in particular in the case of fibers, are able to lower the surface resistance to such an extent that a disruption does not occur due to electrostatic charge during normal use. In the case of fibers, there is also the requirement stated that this reduction in surface resistance is permanent, i.e. that even after a larger number there is an antistatic effect after washing. Because of their effectiveness even in small quantities so far almost exclusively polyether-containing antistatic agents have been used in practice. However, it occurs with polyether Fibers discoloration due to oxidative attack under the influence of light and heat is unpleasant in appearance. Therefore, polyether-free antistatic agents were required which had these disadvantages while being equally effective do not exhibit.

For example, polyamide compositions are already known which, as active ingredients, have low molecular weight polyamides with tert. Contain amide groups (see e.g. German Offenlegungsschrift 1,794,167).

The invention relates to an antistatic polyamide composition consisting of an aliphatic polyamide and 1-30 wt. 96, based on the polyamide mass, a polyester amide composed of recurring structural units of the general formulas

■ C-R -C-R Ii 1 H 2

and

-K-R. -C-R

Il 1 H 0 0

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in statistical distribution,

where ■

Ry, a single bond, a straight-chain or branched alkylene radical, a cycloalkylene or

is an arylene radical,
R ₂ for

-0-CH ₀ -KH V-CH ₀ -O-, -0- <H V-CH ₀ - <H VO-,

0-, -6 | (CH ₂ -CH ₂ -0) _z J,

-Ο + (CH ₂ -CH ₂ -CH ₂ -CH ₂ -O) Λ

or represents the radicals of the general formulas -0-R ₄ -O- and - (0-CH ₂ -CH ₂ ) _y -NH-R ₅ -N- (CH ₂ -CH ₂ -0> _y ,

^R 6

where R ^ is a straight-chain or branched alkylene radical or a 1,4-cyclohexylene radical, R, - is a straight-chain or branched alkylene radical with 2 to 20 carbon atoms, whose chain can also contain tertiary nitrogen atoms, Rg is a short-chain straight or branched alkyl radical with 1 "up to 4 carbon atoms, ζ is an integer from 2 to 30 and y is an integer from 1 to 30,
, for a radical of the general formula -NH-Rc-N-

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where R ₁ - and Rg have the aforementioned meaning, the polyester amides having relative solution viscosities in the range from 1.0 to 4.0 (measured

2? 6X η

on solutions of 1 g substance in 100 ml m-cresol at 25 C).

The antistatic polyamide compositions of the invention are by adding 1 to 30 wt. 96, based on the polyamide mass, of polyester amides from recurring structural units of the general formulas

and

• CR ₄ -CR, -

Il 0

where R.

.4, R ₂ and R, which have the abovementioned meaning and which have solution viscosities in the range from 1.0 to 4.0, are obtained for melts of linear, aliphatic polyamides.

The aliphatic polyamides which lead to the antistatic polyamide compositions according to the invention are linear polyamides or copolyamides, consisting of recurring structural units of the general formulas

CR ^ -C-NH-Ro-NH · II I Il 8 0 0

or

CR ₉ -NHj

wherein

is a straight-chain or branched alkylene radical with 4 to 20 carbon atoms,

a straight-chain or branched alkylene radical, a 1,4-cyclohexylene radical or a radical of Formulas

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CH ₅ -, -CH ₅ - <H V-CH ₅ -, - <H> -CH ~ - <H> -,

-CH

or -CE

is and

for a straight-chain or branched alkylene radical

with 3 to 20 carbon atoms.

Particularly "preferred starting products for the production of the. Antistatic polyamide compounds are polycaprolactam and polyamide. 66.

The addition of the polyester amides to the polyamides can be arbitrary Manner, e.g. by stirring into the melt. According to a preferred embodiment, the melted Polyester amide through an extruder with a metering device of the polyamide melt in the desired Concentration added before deformation. The processing of the melt into moldings, e.g. fibers or foils, becomes not affected by the additives.

The polyester amides used as antistatic additives according to the invention are produced by polycondensation , a stoichiometric mixture of a dicarboxylic acid derivative the general formula

1r

wherein

Is hydrogen or a short-chain alkyl radical with 1 to 4 carbon atoms and

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has the meaning given above and a diol of the general formula H-Rp-H, in which Rg has the meaning given above, together with a primary-secondary diamine of the general formula

N
^R 6

wherein R ₅ and Rg have the meaning given above,

The temperatures chosen are those which allow polycondensation in a reasonable time. In general, the condensation is carried out at from 50 to 300 ^° C. at pressures between 20 atmospheres and 0.001 torr.

According to a preferred embodiment, diol and dicarboxylic acid derivative are used precondensed by known processes, the molar ratio of diol to dicarboxylic acid derivative being 1: 2 amounts to. After adding the diamine, polycondensation is then carried out until the desired viscosity is reached. To recruitment A desired viscosity can be one of the components, dicarboxylic acid derivative, diol or diamine in non-stoichiometric Amount are added, so that a lowering of the average molecular weight results. But it can also be monofunctional Compounds such as monocarboxylic acids, alcohols or amines are used; this procedure prevents that the polyester amides have reactive end groups. A possible Umamldierung when admixing with the polyamides and This makes it more difficult to incorporate them into their polymer chains.

Catalysts are expedient for the production of the polyester amides added, known esterification catalysts such as zinc acetate, antimony trioxide, germanium dioxide are suitable and the same. To a thermal or oxidative

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To avoid degradation of the melt, stabilizers and oxidation inhibitors, such as sterically hindered ones, are also used Phenols or hypophosphorous acid added.

Suitable diols for the preparation of the polyesteramides are e.g. Ethylene glycol, di-, tri-, tetra- and octaethylene glycol, propanediol- (1,3), butanediol- (1,3), butanediol- (1,4), 2,2-dimethyl-propanediol- (1,3) » Hexanediol- (1,6), 2,2,4- and 2,4,4- trimethylhexanediol- (1,6), octadecanediol- (1,12), cyclohexanediol- (1,4), 1,4-bis-hydroxymethylcyclohexane, 2,2-bis- (4-hydroxy-cyclohexyl) methane, 2,2-bis (4-hydroxy-cyclohexyl) propane, Polyether diols such as polytetrahydrofuran, polyethylene glycols, Ν, Ν'-ethoxylated disecondary diamines, such as e.g. N, N'-bis (ß-hydroxyethyl) piperazine. .

As examples of primary-secondary diamines that are used for Her-r Position of the polyester amides can be used, the following may be mentioned:

N-methylethylenediamine, N-methyldiaminopropane, N-isopropyldiaminohexane, N-isobutyldiaminohexane.

As dicarboxylic acids and their derivatives can be used for production the polyester amides, for example, the following compounds are used:.

Oxalic acid ,. Succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid (1.10), Cyclohexanedicarboxylic acid (1,4), isophthalic acid and terephthalic acid or their dimethyl or Diethyl ester. The reaction time for the preparation of the polyester amides is 30 minutes to 20 hours. It will be in an inert gas, e.g. nitrogen. In connection to the condensation under positive pressure or normal pressure-can the pressure can be reduced, generally below 15 torr, the evacuation is particularly suitable for degassing the

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αν, -, '225910Α

Melt.

The antistatic compositions according to the invention can be processed into films and threads by conventional methods.

The relative solution viscosities given in the following examples 77 - were at 25 C on solutions of 1 g substance measured in 100 ml m-cresol.

example 1

In a 500 ml three-necked flask with stirrer, gas inlet tube and distillation bridge, a mixture of 174 parts by weight of dimethyl adipate, 143 parts by weight of octadecanediol (1.12) and 0.45 parts by weight of zinc acetate is slowly heated under nitrogen on a metal bath so that a constant condensation occurs. Once 25Q ⁰ C is reached, 30 minutes is stirred at a pressure of 18 Torr. The precondensate is ^{cooled to 90 0} C, with 44 parts by weight of N-methyldiaminopropane and 3.6 parts by weight of 50 percent. hypophosphorous acid was added and with attached 30-cm column heated slowly to 25O ⁰ C, followed by 30 minutes again evacuated. _{A polycondensate with 7) pel} = 1.36 is obtained which is low in the heat and highly viscous at room temperature.

3.5 parts by weight of the polyester amide are used together with 66.5 parts by weight of a polycaprolactam granulate with Tl ^ g- = 2.70 in the apparatus described above at 270 ^° C., melted and stirred homogeneously. Threads are drawn that are stretched 4.5 times. Their electrical surface resistance becomes more relative after 48 hours of conditioning in a standard climate at 23 ^° C. and 50 %

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Air humidity measured by means of a commercially available high ohm meter (8.10 ¹⁰ ohms, compared to 7.10 ohms without additive) ". The threads are then washed with 5 g / l of an alkaline detergent at 60 ° C in a washing machine and again for 48 hours in a standard climate conditioned After 10 washes

10 a surface resistance of 9 · 10 ohms is measured.

Example 2

258.4 parts by weight Sebazinsäurediäthylester, 45 parts by weight of butanediol (1,4), and 0.45 parts by weight of zinc acetate are condensed in the above-described apparatus under nitrogen to 25O ⁰ C, after cooling, 86 parts by weight of N-isobutyl-1,6-diaminohexane and 3.9 parts by weight 50 percent. hydrophosphorige acid added and polycondensed again to 250 ⁰ C, followed by a 30 minute degassing of the melt at 17 Torr. A viscous, cloudy paste with a relative viscosity of 1.46 is obtained.

In a twin-screw extruder, 6% by weight, based on polycaprolactam, of the polyester amide are added to a melt of polycaprolactam (^ l _re i = 2.70) via a metering screw and spun into a yarn of 85 denier. After drawing and washing, the threads have an upper

10
sheet resistance of 6 · 10 ohms and after the tenth

11 wash on a 1 · 10 0hm.

Example 3

From 174 parts by weight of dimethyl adipate, 31 parts by weight of ethylene glycol and 0.31 parts by weight of zinc acetate is made according to the method described in Example 1 ■ a precondensate and after adding 44 parts by weight of N-methyl-1,3-

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diaminopropane and 2.5 parts by weight 50 percent. hypophosphorous acid produced a polyester amide ('^ qi = 1.28). The product is a slightly cloudy, viscous oil at room temperature. As described in Example 2, 7% by weight, based on the polyamide, are metered into a polyamide 66 melt

('JI, = 2.45). The 4-fold stretched threads prove i / rex. ..Q

the first wash has a surface resistance of 5 · 10 ohms and after 10 washes a surface resistance of 7 · 10 ohms. Untreated polyamide 66 has a surface resistance of 9 · 10 ¹² or 1 · 10 ¹³ ohms.

Example 4

146 parts by weight of adipic acid, 59 parts by weight of hexanediol (1.6) and 0.31 parts by weight of zinc acetate and 79 parts by weight of N-isopropyl-1,6-diaminohexane and 2.9 parts by weight of 50 percent strength. Hypophosphorous acids are condensed analogously to the preceding examples in a two-stage process at 250 ⁰ C and vacuum degassing to a polyester amide with O ^ _rel = 1.37.

100 den silk obtained from polycaprolactam (^ j.qi ⁼ 2.70) with 5% by weight of the polyester amide by metering in a twin-screw extruder shows one after the first wash

8th ·

Example 5

258.5 parts by weight of sebacic acid diethyl ester, 31 parts by weight of ethylene glycol and 0.3 parts by weight of zinc acetate or 79 parts by weight of N-isopropyl-1,6-diaminohexane and 3.7 parts by weight 50 percent Hypophosphorous acids are converted into a polyester amide in a two-step process ("Ί ^ η = 1 | 43)

10
Surface resistance of 8 · 10 ohms, after the tenth wash 7 * 10 ¹⁰ ohms (^ _{rel # of} the threads: 2.64).

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condensed, which is a pale yellowish color viscous paste.

A 7 % ± ge admixture to polyamide 66 and subsequent spinning and stretching to 4.5 times results in threads

10 11

a surface resistance of 9 x 10 6 ohms or 1 x 10 6 ohms

after the first or after the tenth wash O ⁷ JI, _re -i ^{before the} addition 2.45, after 2.36).

Example 6

From 174 parts by weight of dimethyl adipate, 185 parts by weight Octaethylene glycol and 0.54 parts by weight of zinc acetate and then 44 parts by weight of N-methyl-1,3-diaminopropane and 4 parts by weight of 50 p'roz. Hypophosphorous acid is formed by two-stage condensation at room temperature obtained highly viscous, colorless polyester amide.

Polycaprolactam threads, which are 6% by weight of the poly ester amides

contain, have a surface resistance of 9 · 1Cr

10
0hm or 5 * 10 0hm after the first or after the tenth

Laundry.
Example 7

As described in Example 2, 174 parts by weight of dimethyl adipate, 59 parts by weight of hexanediol (1.6), 0.35 parts by weight of zinc acetate, 37 parts by weight of N-methylethylenediamine and 2.7 parts by weight 50 percent. hypophosphorous acid condenses.

Polycaprolactam threads with 5% by weight of the polyesteramide -

10

have a surface resistance of 6 · 10 or 1 »10

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Ohm after the first or the tenth wash. Example 8

230 parts by weight of decanedicarboxylic acid-O, 10), 59 parts by weight of hexanediol -. (1.6) and 0.3 parts by weight of zinc acetate are precondensed in the above-described apparatus under nitrogen to 250 ⁰ C. Then 44 parts by weight of N-methyl-1,3-diaminopropane, 3.3 parts by weight 50 percent. hypophos · phorige acid and to establish a particular molecular weight, 8 parts by weight of N-methylstearylamine added and maintained at 250 ⁰ C with a polyesteramide nrt __ _Ί = 1.21 as a viscous product.

Polycaprolactam threads, which comprise 8% by weight of the polyester amide

10 hold, have a surface resistance of 4 x 10 or 8 · 10 0hm after the first or after the tenth wash.

Example 9

194 parts by weight Isophthalsauredimethylester, 143 parts by weight 0ctadecandiol- (1.12) and 0.51 parts by weight .Zinkacetat are precondensed to 270 ⁰ C. After adding 79 parts by weight of N-isopropyl-1,6-diaminohexane, 10 parts by weight of dodecanoic acid and 4.3 parts by weight of 50 percent strength. hypophosphorous acid is condensed to 270 ⁰ C and polyesteramide as a brittle glass-like product was obtained ( 'Ί, = 1.61).

Polycaprolactam threads with 10% by weight of the polyesteramide

11 have a surface resistance of 1 · 10 or 2 · 0hm after the first or after the tenth wash.

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194 parts by weight of dimethyl terephthalate, 185 parts by weight of octaethylene glycol and 0.57 parts by weight of zinc acetate or 44 parts by weight of N-methyl-1,3-diaminopropane, 8 parts by weight of methyl stearate and 4.3 parts by weight of 50 percent by weight. ^{Hypophosphorous acids are condensed up to 270 °} C. in each case in a two-stage process. _{The polyester amide} is glassy, brittle (^ Γβ ι = 1 »54) and colorless.

Threads made of polyamide 66 with 10% by weight of this polyester amide

1 (V show a surface resistance of 2 · 10 ohms the first or after the tenth wash.

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Claims (1)

Patent claims: in statistical distribution,
wherein
R _{1 is} a single bond, a straight-chain or branched alkylene radical, a cycloalkylene or is an arylene radical, R _{2 stands} for the radicals -0-R ^ -O-, -0-CH ₂ - / H VcH ₂ -O-, -0- / H N-CH ₂ - / H \ -0-, 0-, -0- (CH ₂ -CH ₂ -O) ₂ - -0- (CH ₂ -CH ₂ -CH ₂ -CH ₂ -O) _z or for the radicals of the general formulas -0-R ₄ -O- and - (0-CH ₂ -CH ₂ ) -NH-R ₅ -N- (CH ₂ -CH ₂ -O) y- is where R / is a straight-chain or branched one Alkylene radical or a 1,4-cycloalkylene radical, Re straight-chain or branched alkylene radical with 2 to 20 carbon atoms, the chain also may contain tertiary nitrogen atoms, Rg a Le A14 744 - 14 - 409823/0975 short-chain straight or branched alkyl radical with 1 to 4 carbon atoms, ζ is an integer from 2 to 30 and y is an integer from 1 to 30,
R, for a radical of the general formula -NH-Rc-N- ^R 6 stands in which R, - and Rg have the aforementioned meaning own and where the polyester amides have relative solution viscosities % _Te - \ in the range from 1.0 to 4.0 (measured on solutions of 1 g of substance in 100 ml of m-cresol at 25 ° C.). Process for the production of antistatic polyamide compositions by adding antistatic compounds to polyamides, characterized in that 1 to 30% by weight, based on melts of linear aliphatic polyamides on the polyamide mass, on polyester amides from recurring structural units of the general formulas CR ₁ -CR ₂ 4 0 and clogs, wherein R _{1 is} a single bond, a straight chain or a branched one. Alkylene radical, a cycloalkylene or is an arylene radical, R _{2 stands} for the radicals -0-R ₄ -O-, 0-CH ₂ - / H VcH ₂ -O-, -0- / H VcH ₂ - / h) -0-, -0-, -0-J (CH ₂ -CH ₂ -O) ₂ I, Le A14 744 409823/09 7 "5th -Oj- (CH ₂ -CH ₂ -CH ₂ -CH ₂ -O) _z j or represents the radicals of the general formula -O-Ra-0- and - (0-CH ₂ -CH ₂ ) -NH-R ₅ -N- (CH ₂ -CH ₂ -O) -, where R ^ is a straight-chain or branched alkylene radical or a 1,4-cycloalkylene radical, Rc is a straight-chain or branched alkylene radical with 2 to 20 carbon atoms, the chain of which can also contain tertiary nitrogen atoms, Rg is a short-chain straight or branched alkyl radical with 1 to 4 carbon atoms, ζ is an integer from 2 to 30 and y is an integer from 1 to 30,
R, for a residue of the general formulas -NH-Re-N- stands in which R, - and Rg have the aforementioned meaning own and wherein the polyester amides have relative solution viscosities in the range from 1.0 to 4.0 (measured on Solutions of 1 g substance in 100 ml m-cresol at 25 ° C). 3. threads and films made from polyamide compositions according to claim 1. 4. Use of polyester amides made from recurring structural units the general formulas CR ₁ -CR ₉ I.
Ii 1 H 2 O O and Le A14 744 - 16 - 09823/0075 wherein R ^, Rp and R-. have the meaning given in claim 1 and the solution viscosities in the range of
Have 1.0 to 4.0, in amounts of 1 to 30 wt.%, Based on the polyamide mass, as antistatic agents for
high molecular weight, linear aliphatic polyamides. ORiQmAL INSPECTED Le A14 744--17- ° ^ 409823/0975