DE1569596C3 - Molding compounds - Google Patents

Description

wherein R is an alkyl radical having 8 to 18 carbon atoms, Ri is the group '5

-CH ₂ -CH ₂ - (OCH ₂ CH ₂ X _n OH

where η is O or 1, R _{2 is} a hydrogen atom or has the same meaning as Ri, or the quaternary ammonium salts thereof, this antistatic agent in an amount of 0.05 to 5%, based on the weight of the polymer, is available.

2. Molding composition according to claim 1, characterized by a content of

N- (2-hydroxy-3-dodecyloxypropyl) -

ethanolamine. or

N- (3-dodecyloxy-2-hydroxypropyl) -N, N-bis (2-hydroxyethyl) -

N-methylammonium methosulfate

as an antistatic agent.

35 and can be easily incorporated into them during conventional compounding and milling stages. The antistatic properties of the medium must be practically permanent and also withstand high temperatures. The thermal stability is particularly important for use in polypropylene, which has to be heated to high temperatures for compounding, grinding and shaping.

The substances used so far met some of these requirements to varying degrees. Nevertheless there is a definite need for a practical antistatic agent that is used in. is effective at low concentrations and has good thermal stability, so that its effect is not destroyed during the processing stages. This need is now satisfied according to the invention.

The molding compositions according to the invention are composed of a polymer and an antistatic agent characterized by the content of a compound of the formula

OH Ri

R-OCH ₂ -CH-CH ₂ -N _r :

Polymers, such as homopolymers and copolymers of ethylene, propylene and butylene, tend to be Manufacture and subsequent use of static electricity, resulting from a number of Reasons is extremely disadvantageous. Charged bodies attract dust, and so can others cause disruptive effects, such as electric shocks to the person who touches the charged material, or Radio interference interference.

Various means of avoiding or minimizing static electricity have been used proposed how to apply various types of antistatic substances, such as quaternary ammonium salts, on the respective surfaces. Such a surface treatment, however, often only sets in Temporary aid. The application of antistatic coating compounds has also already been carried out proposed such surfaces. However, such coating processes are costly and beneficial no lasting effect. Finally, the incorporation of antistatic agents into the respective Plastic compound proposed during the compounding, shaping or manufacturing stages. Out For practical reasons, an antistatic agent that is to be incorporated directly into the plastic must be meet certain requirements. It must be used in reasonable concentrations be sufficiently statically active and work at low concentrations without affecting the Worsen the properties of the polymer. The material must be compatible with the plastic compound wherein R is an alkyl radical having 8 to 18 carbon atoms, Ri is the group,

- CH ₂ - CH ₂ - (OCH ₂ CH ₂ ) "OH

denotes, where η is 0 or 1, R _{2 is} a hydrogen atom or has the same meaning: as Ri, or the quaternary ammonium salts thereof, this antistatic agent in an amount of 0.05 to 5%, based on the weight of the polymer , is available.

The molding compositions according to the invention preferably contain antistatic agents

N- (2-hydroxy-3-dodecyloxypropyl) -.

ethanolamine, or

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

N, N-bis (2-hydroxyethyl) -

N-methylammonium methosulfate.

In normal areas of application, the antistatic is used used in concentrations of 0.3% to 2.0%. The antistatic agents used in the present invention are unusually highly thermally stable compared to the previously used antistatic, as above already outlined what is an essential requirement for useful antistatic agents for plastics This property can be shown in various ways, for example by assessing the discoloration; Exercise or decomposition of a plastic compound that contains the antistatic compounds. In some cases The antistatic agent even accelerates the decomposition of the plastic if the antistatic agent is used containing mass is exposed to progressively elevated temperatures. With the agents used according to the invention, however, this effect becomes complete significantly reduced.

There are several methods of evaluating the compounds used in the present invention as antistatic Funds available. Molded or extruded batches of polymers that have a known

Amount of antistatic agents contained were prepared and then checked for heat resistance and Surface resistance investigated.

The antistatic agents used in the present invention can be ordered by adding an alcohol Reacts a suitable chain length with epichlorohydrin to form a 2-hydroxy-3-chloropropyl ether, this product is treated with sodium hydroxide to form glycidyl ether, and this ether is then treated with converts an alkanolamine to form the tertiary dihydroxyethylamine, which then, if desired is quaternized to quaternary salts.

The alcohol used for this purpose, which contains a suitable amount of a Lewis acid catalyst, such as tin dichloride, Aluminum chloride, zinc chloride or similar compounds, but preferably tin (IV) chloride contains, the amount between about 0.1 and about 1.0%, preferably 0.25 and 0.75%, based on the Weight of the starting alcohol, is added at room temperature with the slow addition of epichlorohydrin, stirred for a period of about 2 hours. The temperature and the speed the addition of epichlorohydrin can vary within wide limits, but this results in the case of those specified Conditions for minimal color formation, by-product formation, volatilization of the starting materials, as well as optimal reaction control. The theoretically required molar ratio of alcohol to epichlorohydrin is 1: 1. However, to avoid the possibility of reacting more than one mole of epichlorohydrin with However, to keep the same alcohol molecule to a minimum, it is preferred to keep the alcohol in one Use an excess of about 5 to 50 mol%, preferably in an excess of 10 to 35 mol%.

After complete addition of the epichlorohydrin as described above to the starting alcohol, the Reaktfonsgemisch to about 70 to 15O ⁰ C, preferably 90 to 110 ⁰ C, for about 1 to 4 hours, preferably 2 to 3 hours is heated, and then cooled. A practically colorless oil is obtained. "'"^;

The product obtained in this way is treated with sodium hydroxide in a suitable organic solvent without purification or, if necessary, after purification, since it contains excess alcohol, wherein ^; the amount of alkali used is equivalent to the amount of epichlorohydrin used. Suitable inert organic solvents include petroleum hydrocarbons, ethers, benzene, toluene, xylene, ketones, and the like. The inert solvent; should have a boiling point above 'of about 8O ⁰ C. Di-n-butyl ether (boiling point 142 ° C) has been used with great success. The existing amount of the solvent can be widely from about 100 to about 200.%, based on the weight of the at .l;. Reaktibnsgemisches obtained, process step variieren.- The reaction mixture is heated to a temperature between about 70 and 130 ⁰ C. , preferably 80; to: .110 ⁰ Cv. during:; -., heated for about 2 to 4 hours, preferably 2.5 to 3.5 hours. The mixture is then cooled, filtered, washed with water and dried over anhydrous sodium sulfate. The mixture is then heated to evaporate the solvent and the residue is distilled under reduced pressure. The fraction with a suitable boiling range at the pressure used is collected and cooled. The product, which is generally a colorless light oil, consists of the glycidyl ether.

The glycidyl ether thus obtained is stirred with

an alkanolamine reacted in approximately equal molar proportions. When the exothermic reaction subsided the mixture is cooled. The product, in

generally a viscous colorless oil, represents the with a tertiary amine substituted ether.

Usable amines for the preparation of the above,

ίο Amine-substituted ethers are di - (/? - hydroxyalkyl) amines, the alkyl groups of which contain 1 to 6 carbon atoms. Secondary amines with either hydroxyethyl or hydroxypropyl substituents are particularly valuable. ^:

The amine-substituted ether obtained in this way is now, if an alkylene oxide adduct is desired, with Ethylene or propylene oxide reacted under the usual conditions for the production of alkylene oxide adducts About 2 to 20 moles of the alkylene oxide are converted per mole of ether. : ■ ■

The tertiary amine ether obtained in the manner described above can be quaternized with a suitable agent such as methyl chloride, ethyl chloride, dimethyl sulfate, diethyl sulfate and the like. The amount of quaterrifying agent is generally equimolar to the amount of tertiary _: Amino ethers ,. however, a slight deficit of this agent can be used to avoid the presence of unreacted quaternizing agent in the final product. The quaternization is carried out in the presence of a suitable inert organic solvent as described above, for example acetone. If acetone is used as the solvent, heating to reflux temperature is sufficient for this reaction. The solvent is then removed to give the desired hydroxyalkyl quaternary ammonium ether generally as a white waxy material.

The preferred quaternizing agent consists of dimethyl sulfate. The preferred anions of the quaternary Compounds are methosulfate and fluoroborate. The former kind of anions is obtained directly when Dimethyl sulfate is used as a quaternizing agent; the latter type is made by anion exchange using a suitable salt of the desired acid or by reacting the quaternary Combination with alkali to produce the free base and subsequent acidification with the appropriate one

Acid received. ^. ^ i ^ K - ^ 'b; - ^ ^r ö ^: · -V- ' ■■■■■ ^:: - "J ^ r ^ -

Production of N- (dodecyloxy-2-hydroxy-

propyl) -N, N-bis (2-hydroxyethyl) -
- N-methylammohium'methosulfat

. ■ ■ ^.; -:;: - 6 - HsiV-

A mixture of 276 g of 1-dodecanol and 1.0 g of tin (IV) chloride was held in a suitable reaction vessel at 25 ° ^C: stirred while 92.5 g of epichlorohydrin were added over 2 hours. After the addition had ended, the reaction mixture was heated to 100 ° C., kept at this temperature for 2 hours and then cooled. Practically colorless oil was obtained. ^y Ί

The above mixture was treated with 50 g of powdered sodium hydroxide in 500 ml of di-n-butyl ether. The mixture was ^{heated to 90 °} C., kept at this temperature for 3 hours, cooled and filtered. The filtrate was washed with water

1 b by

washed and dried over anhydrous sodium sulfate.

The dried filtrate was placed in a reaction vessel equipped for vacuum distillation and then heated.

The solvent was removed and then the one at 140-145 ° C with 0.15 mm of mercury appropriate pressure boiling fraction collected. The product consisted of a colorless light oil.

A mixture of 282 g of the product thus obtained and 105 g of diethanolamine was stirred while heating on a steam bath. An exothermic reaction increased causing the temperature to 135 ⁰ C. After the exothermic reaction had ceased, the product was cooled to give a colorless viscous oil.

63.0 g of dimethyl sulfate in 500 ml of acetone were added to 193 g of the above product. the Solution was heated to reflux and immediately cooled. The solvent was raised by heating removed in a steam bath. The product consisted of a white waxy material.

The corresponding ethylene oxide adduct with 10 moles of the oxide was made from one mole of N- (3-dodecyloxy-2-hydroxypropyl) -N, N-bis (2-hydroxyethyl) -N-methylam- Monium methosulfate produced by about 12.5MoI of the oxide were blown in under slightly increased pressure. The speed of the encore is that the reaction mixture remains at a moderate reflux temperature.

Production of

N- (2-Hydroxy-3-dodecyloxypropyl) ethanolamine agent A.

C ₁₂ H ₂₅ OCH ₂ CHCH ₂ NHCH ₂ CH ₂ Oh OH

In a suitable vessel were 242 parts (1.0 mol) of 2,3-epoxypropyl-n-dodecyl ether and 61 parts (1.0 mol) Given 2-aminoethanol. The mixture was heated on the steam bath for 2.5 hours. The product was then cooled and recrystallized from hexane. The product differed as a white plate-like one Solid with a melting point of 59 to 60 ° C.

Additional connections were made using the same procedure but using different 2,3-epoxypropyl ether and other ethanolamines produced, as can be seen from the following examples:

obtained product was a liquid with a boiling point of 212 to 215 ° C at 0.3 mm Mercury appropriate pressure.

The ethylene oxide adducts of agents A, B and C were by the corresponding reactions of Compounds A, B or C with 6 moles of ethylene oxide in the presence of sodium methoxide at one temperature of about 125 ° C and a pressure of 1.76 atm.

example 1

Test samples were made by mixing and

Milling of the additives according to the invention in various polymers are produced and then subjected to extrusion molding. The following were

de antistatic agents used: -:

Middle A: r ^

N- (2-Hydroxy-3-dodecyloxypropyl) -;:

'ethanolamine. ·: ^.

Medium B:. ■

N- (2-Hydroxy-3-dodecyloxypropyl) diethanolamine. -

Means C: ·: '_; r ^: -

N- (2-hydroxy-3-dodecyloxypropyl) -. 2- (2'-hydroxyethoxy) ethylamine.

Medium D:

N- (2-Hydroxy-3-octyloxypropyl) ethanolamine.

Means E:

N- (2-Hydroxy-3-octyloxypropyl) -2- (2'-hydroxyethoxy) ethylamine.

Middle X:

Commercial ethylene oxide adduct of a long-chain alcohol.

N- (2-Hydroxy-3-dodecyloxypropyl) diethanolamine agent B.

Manufactured by reacting 2,3-epoxypropyln-dodecyl ether with diethanolamine. The product was obtained as a liquid with a boiling point of 213 to 218 ° C. at a pressure corresponding to 0.2 mm of mercury . ; _; . .: .: ■ - ■ ': ■ -V "

Production of N- (2-hydroxy-3-dodecyloxypropyl) -2- (2'-hydroxyethoxy) ethylamine

- '■■. ■ ... ".. - - _: MediumC- · = ■■ :: <: ■ _r ■■: ■■' :

Manufactured by reacting 2,3-epoxypropyln-dodecyl ether with 2- (2'-aminoethoxy) ethanol. The Evaluation process and results

The compounds were selected for their suitability "as antistatic agents for various polymers using the test methods described below, examined: The test samples were / conditioned for 24 hours at 50% relative humidity The antistatic activity was then determined in the following way:

1. Determination of the surface resistance,

2. Cigarette ash test, where the sample is rubbed 20 times with a woolen cloth and the distance in cm over which the film shows attraction; = for cigarette ash is determined * No ash uptake up to 2.5 cm indicates good antistatic properties. '' ■■ i; "» ^; si '·

3. Electrostatic finder experiment, in which the sample is rubbed 20 times with a woolen cloth and placed = 2.5 cm away from the probe of the instrument. The instrument measures the amount of charge on the surface of the plastic / lower values indicate good antistatic properties. ^: ' ^l - ^: ' - ^: '' ^

The results of the experiments are summarized in Table I below. ; '· ^::

Table 1

Antistatic Properties of Various Extruded Films

No. Polymer Antistatic agent ?., Antistatic tries Electro Surface Ash attempt more static resistance Button (%) (Megaohm) (cm) 500 1 Polyethylene without 50 · 10 ⁷ 12.7 75 high density Medium A (0.5) 15 · 10 ³ 0.6 250 Medium B (2.0) 90 · 10 ² 1.27 100 Middle C (2.0) 35 · 10 ² 0 0 Middle D (0.5) 60 · 10 ² 0 5 Mean E (0.5) 65 · 10 ² 0.6 300 Medium X (0.5) 25 ■ 10 ⁶ 7.6 600 2 Polyethylene without 15 · 10 ⁷ 7.6 25th low density Medium A (0.3) 22 · 10 ³ 1.27 0 Middle B (0.5) 25 · 10 ³ 0 600 3 Polypropylene without 50 ■ ΙΟ ⁷ 11.4 0 Medium A (2.0) 30 · ΙΟ ³ 0 50 Middle C (2.0) 21 · 10 ⁴ 2.5 400 Medium X (2.0) 50 ΙΟ ⁵ .5.1 700 4th Polystyrene without 15 · 10 ⁷ 10.2 50 Medium A (1.5) 25 · 10 ³ 1.27 60 Medium B (2.0) 30 · 10 ³ 1.27 350 5 Polystyrene without 20 · 10 ⁷ 10.2 25th Butadiene copolymer Medium A (2.0) 14-10 ⁴ 0.6 500 6th Acrylonitrile butadiene without - 5.1 100 Polymer Middle C (2.0) 55 · 10 ⁴ .1.9 - 7th Polyvinyl chloride (stiff) without 50 ⁷ - - Medium B (3.0) 11 10 ³ - _ Middle C (2.0) 11 · ΙΟ ⁴ -

Ex

The additives were incorporated into certain polymers on the mill. The milled material was granulated and extruded at 175 to 260 ° C in the case of low density polyethylene and at 200 to 290 ⁰ C for high density polyethylene and polypropylene. In the case of high density polyethylene, 0.5% titanium dioxide was added to the polymer during compounding to determine its influence on the antistatic properties. ........

During the extrusion process, which is carried out by a

ie

moderate to heavy smoke formation is accompanied, there was no separation of the substances used according to the invention Compounds observed on the take-up rollers, as is the case with many previously known antistatic Means is.

The antistatic properties were determined in the manner given above; the results are summarized in Table II below. > ■■■ - * ^-:; .

Table II of extruded films, as well as TiO ₂ pigmented polymers tries Electro Antistatic properties Grayling attempt more static (Concentration 0.5%), Antistatic agent concentration Antistatic Button No. of polymer type Surface resistance ..... _; '.; (cm) ·.; -. ^;,;:: .'I: i 850 · "· - ■" ■■ · ■ ■ ■;. '.' ■ ■ '"■' 15.2: - ■ '- .: ^~: .50; (%). ■■? /. ■ - .. · ■ O 150 without ;. 50 -10 ⁶ 0 . 0 1 polyethylene Means A 0.25 ■ /. · ■■ "■ .. 15 · 10 ² 0 609 553/406 (low density) Medium B 0.25 25 · 10 ² Medium X 0.50. · .. ■ • 12. ·. 10 *

Polymer type 9 15th 69 596 Antistatic 10 Electro 0 Surface more static 0 resistance tries Button 700 Antistatic agent concentration Ash attempt continuation 750 No. Polyethylene 30 · 10 ⁶ 20th (high density) 15 · 10 ² (cm) 20th (%) 20 · 10 ² 15.2 15th without 16 · 10 ² 0 400 Means A 0.3 19 · 10 * 0 - 2. Polypropylene Medium B 0.3 50 · 10 ⁷ 0 Middle C 0.3 30 · 10 ² 7.6 Medium X 0.5 20 · 10 ³ - without - - 0 Means A 0.75 0 3 Middle C 0.75 20.3 Medium X 0.75

These values show that the compounds used according to the invention are valuable antistatic Means under extrusion conditions are that they are heat stable and their activity by presence from T1O2 will not be worsened and will be more effective than a commercially available antistatic agent are.

Example 3
■ Thermal stability tests

N- (2-Hydroxy-3-dodecyloxypropyl) ethanolamine was subjected to thermal differential analysis and thermogravimetric analysis. The results of the 1st experiment show that this compound is heat-stable up to 300.degree. In the second experiment, it was found that volatilization of the compound was carried to the extent of 10% of the amount originally present, if the temperature was gradually increased to 261 ⁰ C. Together with the former result, this result indicates that the compound volatilizes without decomposition within the examined temperature range.

Continued to show a sample of high-density polyethylene, containing 0.5% of this additive, excellent heat stability, during a period of 30 minutes at 230 G ⁰ in an apparatus for determining the melt index. The discoloration that occurred was not worth mentioning.

Example 4

According to the invention. became . Additives in one Copolymer of 80% vinyl chloride and 20% vinyl acetate in various concentrations by grinding on a two-roll laboratory mill at 175 ° C incorporated for 5 minutes. The obtained milled sheets were heated at 170 to 175 ° C and a pressure of 24 t press-formed into plates of 5 χ 6.3 χ 0.127 cm. The antistatic properties were measured at a relative humidity of 50, 40 and 20% (R.H.) determined by determining the surface resistance and are listed in Table III. For comparison purposes were samples without addition (control) and with an equal concentration of lauramidopropyldimethyl-ß-hydroxyethylammonium methosulfate, a commercially available antistatic agent, was also examined. The thermal stability was enhanced by the The extent of the discoloration of the polymer determined during grinding and aging in the oven 175 ° C was observed and is in Tables IV and V compared with the same commercially available antistatic agents listed.

Table III

additive Conc Surface resistance 40% R.H. (Megaohm) tration N. U. (%) SOVc 60 ■ 10 ² 20% R.H. example 1 1.5 40 · 11 · 10 ³ N. U. 0.5 17 · N. U. 30 · 10 ³ 0.3 58 · N.W. 60 -10 ³ Trade 1.5 40 · N.W. N. U. usual. 0.5: - 20 · N. W. - antistatic 0.3 N. ¹ N.W. Medium '.·. , R. H. 10 10 ² ■ 10 ² . 10 10 ⁷ W.

"NU" means "not examined".
"NW" means "not effective".

Table IV r ;, ::

Thermal stability at 175 ^{0 C:}
Aging on the mill at 175 ⁶ C
1.5% antistatic agent

Enjoy the meal Discoloration Commercial means (Min.); R = C ₁₂ H ₂₅ - -. hardly yellow 5. -. .. hardly yellow ■ ; very pale yellow 10 very pale yellow ; light yellow 15th light yellow dark yellow 20 - ■■ - ": ';; yellow strong 'thin 23 not examined 'geiborähge ^! not examined 25th yellow-orange not examined 30th dark orange

11 12

Table V

Compound aging in the oven at 175 ° C VYNS (approach as above)

Discoloration after the following number of minutes 6 12 18 24

R = Q ₂ H ₂₅ - light yellow yellow yellow orange dark red

Commercial agent light yellow dark orange black not investigated

Example5

When examining the additive of Example 1 in rigid polyvinyl chloride following the procedure of Example 6 the following results were obtained:

0.3% additional yellowing index 50% R. H. '40% R. H. 30% R. H.' 20% R. H.

R = C ₁₂ H ₂₅ 3 15 · 10 ² 34 · 10 ² 16 · 10 ³ 13 · 10 ⁴

'B ei s ρ i e 1 6

Rigid polyvinyl chloride pigmented with 5.0% TiO _{2 was} investigated according to the procedure of Example 6 using the additive according to Example 1. The following results were obtained:

0.5% Antistatic Agent Yellowing Index Resistance (Megaohm) '

50% R.H. 40% R.H. 20% R.H.

R = C ₁₂ H ₂₅ '1 12 · 10 ² 10 · 10 ³ 36 · 10 ⁴

Claims (1)

Patent claims: 1. Molding compositions composed of a polymer and an antistatic agent, characterized by the content of a compound of the formula OH R-OCH ₇ -CH-CH, -N R,