DE1948201A1 - Antistatic phosphorus compounds - Google Patents

Description

The present invention relates to new antistatic phosphorus compounds, the electrostatic charging of synthetic and natural fibers, such as polyester fibers, Avoid cellulose acetate, rayon, wool, polyolefins or similar fibers. In particular, this relates to Invention substituted phosphonamides with antistatic properties by reacting alkyl or aryl polyethylene oxychlorophosphates with substituted alkyldiamines and subsequent treatment with acid and alkoxylation getting produced.

The industrial importance of synthetic fibers has also increased the importance of antistatic agents and coatings, the synthetic fibers that generate static electricity, e.g. polyester, acrylic or vinyl fibers, etc., are necessary are. While fibers such as cotton or viscose have practically no static electricity in normal humid conditions With fibers like acetate, rayon and wool only massive amounts of charge

009816/1891

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effect and therefore only a few in the processing plants Precautions are synthetic Fibers are not easy to handle in order to keep the electrostatic charge under control.

Various non-durable coatings have been proposed which produce unsatisfactory electrostatic charges impede; only a few of them are satisfactorily effective. Most of the coatings used are electrostatic Preventing charging fall under the category of pure surface treatment agents, although there is no relationship between them There is surface activity and an antistatic effect.

In general, antistatic agents work in two directions, however, both of which improve the electrical conductivity of the paser surface. Either they are remarkable themselves good conductors of electricity or they are hygroscopic and thereby cause moisture to accumulate on the Fibers.

The majority of antistatic agents fall under one of the the following categories: 1) nonionic compounds of the polyhydroxy or polyethyleneoxy type; 2) cationic or neutral nitrogen compounds with a hydrophobic part in the structure of the compound} 3) long-chain phosphates, Phosphonates or other oxidized phosphorus derivatives. Other Types are sulfonated oils and ester emulsions or others Fiber-lubricating oil emulsions based on the special antistatic effect of the emulsifier used.

Long-chain, quaternary ammonium salts have a remarkable antistatic effect and are used because of this property used a lot. These quaternary ammonium salts, which are often contained in antistatic coatings, are often used in conjunction used with aids that can söin themselves antistatic or serve a further purpose, namely the

0 0 9 816/1891

-3-

- sheet 3 -

To make the coating adherent to the paser. Such connections are described in U.S. Patent 2,46,282. Water soluble Salts of higher molecular weight amines with polystyrene sulfonates c - '. R.d in US Pat. No. 2,700,001 as Eylon antistatic agents

wrote. The use of phosphorus compounds as antistatic agents is described in U.S. Patents 2,575,382, 2,57p, and 2,676,122. Hygroscopic salts such as Cycloliexylaninl ^ are CTAT is vährend described in German Patent 840 694 discloses the use of polyethoxylated fatty acids and alcohol eo as an antistatic agent for PolypropylenrL in US Patent 2,525,691.

23 it has now been found that compounds which contain a phosphonamide structure in the molecule, in particular phosphonanide compounds which have been prepared by reacting a calcium phosphonate of an alkoxyated primary or secondary alcohol or alkylphenol with a gamma-dialkylaninopropylamine, Has excellent anti-static properties when applied to synthetic fibers. The new Pbospfionawide give the. Fibers aenschaften not only because of their Aniidbindung or your QuaternärstriiKtur antistatic properties, but also the g, evfönschten egg and characteristics of poüyä'thox.ylierten Hydrophoben- Uaerwarteterweise you erhKlt just 4urch the combination of these chemical features in a PhoBphonamidmoleküJ Superior effects against antistatiEchen means consist of mixtures of non-ionic compounds and amides.

oils have new anti-static compounds the general formula

R-O (CH,. CHO)

IU

I!

—-P-

NH-CH ₂ CH ₂ CH ₂ -MR ₂

009816/1891

BATH ORIGINAL

- sheet 4- -

in which R is an alkyl or alkaryl radical with at least 7 carbon atoms, X is hydrogen or a methyl or ethyl radical, R ₁ and R _{2 are} alkyl or hydroxyalkyl radicals with 1 to 5 carbon atoms, R is a hydroxyalkyl radical with 1 to 4 carbon atoms , Y is an anion, m is an integer from 1 to 10, η 1 or 2 and ρ 1 or 2.

In particular, R should mean the following alkyl or alkaryl radicals: Heptyl, Gcöyl, Xo-iyl, Decyl, Undecyl, Dodecyl, Tridecyi, Hexadecyl., Öc-c & decyl, methylphenyl, ethylphenyl, butylphenyl, Hexylphe ::; .. 1., Octylphenyl, Nonylphenyl, Decylphenyl, Dodecylphenyi, i? entadecylphenyl, octadecylphenyl, nonadecylphenyl

^ or Pher.yl.

iJls Examples of alkyl or hydroxyalkyl radicals R, and R ₀ may be mentioned are: methyl, Ilohyl-, propyl, isopropyl, hydroxymethyl, Hydroxyathyl-, hydroxypropyl or dihydroxy propyl radical.

As an example, for Eydrc- ^ alkyireste R, are mentioned: der Hydr.; ^ - ^ oühyl-, Hydroxyethyl-, Hydroxypropyl-, Hydroxybu "cyl-. ^ hydroxypropyl or dihydroxybutyl radical.

Anions Z which can be used according to the invention are: halides (Chloride, bromide, iodide), phosphates, nitrates or sulfates.

The new phosphonamides of the invention are also used. . .lkyl- or arylpolyäthylenoxychlorphosphonaten with or.3n substituted alkyldiamine and subsequent treatment with acid and alkoxylation produced. According to a preferred production method, a commercially available mixture of straight-chain aliphatic alcohols, which contains approximately 5 % C ₁₁ , 25 % C ₁₂ , 30% C ₁₅ , 30% C ₁₄ and 10 % G ^ , with an alkylene oxide is used an alkaline catalyst at 120 to 15O ⁰ C and a pressure of

BAD ORiGfNAL -5-

009816/1891

0.07 "to 2.1 kg / cm ^ until 1 to 10 moles of oxide are absorbed have been. Instead of the alkaline catalyst, acidic catalysts such as BF ,, H-JPO ^, and the like can also be used be used. Instead of the primary aliphatic alcohols, secondary alcohols such as 2-decanol, 5-decanol, 4-decanol, 3-dodecanol, 4-lev ^ decanol, 6-hexadecanol, etc., or their mixtures, as well as alkylphenols such as octylphenol, linear decylphenol, branched dodecylphenol, etc. are used will. The restrained alkyl or alkylaryl polyalkyleneoxyalkanol is then reacted with phosphorus oxychloride, whereby the corresponding mono- or di-alkyl or alkaryl polyalkylene oxychlorophosphonate arises. The compound obtained last is obtained by reacting it with gamma-dialkylaminopropylamine in | das en-jsprecher.de converted to phosphonamide. The obtained phosphonane ^ u is then acidified and reacted with alkylene oxide, whereby the quaternary ammonium salt is formed.

The reaction described above proceeds generally in accordance with the following reaction equations:

I. i.0H + alkylene oxide catalyst> R.

II. RO (CH ₂ CKO) _m + POCl ₃

RO (CH ₂ CH)

POCl _2. + HCl

In general, equivalent amounts of the starting materials are used. Phosphorus oxychloride is added dropwise to the ethoxylated mixture with stirring until the conversion is almost theoretical.

The alkyl or alkaryl polyalkylene oxychlorophosphonates are then further treated with substantially equivalent amounts of gamma

-6-009816 / 1891

BATH

- sheet "6 -

Dialkyl or dialkanolaminopropylamine implemented, with substituted Amides are formed according to the following reaction equation:

III. RO (CHCHO) POCl + HH (ClO HJ ^ i * ¹

2 ι 2 m X

RO (CH .CHO)
2 ι

P.

nh (ch ₂ ) _a -n;

The substituted amides prepared according to equation III can then be substituted by reaction with an alkylene oxide or hydroxy Alkylene oxide can be quaternized in the presence of an acid, as the following equation shows:

IV. RO (CH ₂ CHO) _1n

L χ.

Ii

-P-

NH (CH ₂ ) _A -N

+ Alkylene oxide + EZ

ROH (CH ^ CHO)
21 m

Il

- P-

-i +

HH (CHL) -N

^{2 A}

In the above 6β ^η β »Λ * βΣΐ equations E, R ₁ , Rg» R ^ »X, m, n, P and Y have the meaning given at the beginning of the description and A means an integer from 1 to 5 ·

-7-

009816/1891

- sheet 7 -

The novel "compounds of the invention have unexpectedly advanced antistatic properties, especially when applied to synthetic fibers such as polyester, acrylic, polyolefin or polyamide-IT fibers. They reduce and keep electrostatic charge below y kilovolts for extended periods of time .

The following examples describe the invention.

a) In one. 288 parts by weight (1.85 mol of EO) of ltlioxyla-υ, which consists of a mixture of straight-chain primary C ₁ ^ -C- _; -Alcohols Liit has an average molecular weight of 209 stem and the following composition: 5 % 0 -, -, 25 % ^, "> 0 ^c / o C ₁ -, 3o% G ₁ ^ and 10 % C _15. The ethoxylate is at

5O ⁰

20 b: .3 50 ⁰ G stirred and added within 1.5 "to 2

77 parts (0.5 mol) of phosphorus oxychloride are added dropwise to the addition of the phosphorus oxychloride, the mixture is heated to 70 ° C. and at this temperature for one hour. Thereafter, one hour at the same temperature

ojickstoff dur.ch managed the mix. After that, in Distance samples taken from the mixture until that of the hydrolyzed sample is as low as theoretical

r ^ ö ^ i-cli is.

b ' _y Ζλ a flask equipped with a stirrer, two dropping funnels, Thermo-ZC-WÖL- · and pH meter, 500 milliliters of jcr and 91 g (0.9 mol) of dimethylpropylenediamine are added. To ... ..εοΓ mixture are added with stirring at room temperature within about one to 1.5 hours at the same time 591 g (0, ^ rioii.) Of the chlorophosphonate described under (a) and 30 % - ije KixOH at a rate, that the pH of the mixture is between 10.5 and 11.0. A total of 150 g of JO- $ oige NaOH are required. After all the reactants have been added, the mixture is left at room temperature for 15 minutes.

-8-009816 / 1891

BATH ORIGINAL

- sheet 8 -

stirred and then adjusted to pH 9.0 with HCl. A total of 12.0 g are required for this. The product is then freed from water at a pressure of 40 mm and the residue is filtered. The yield is 557 g. (85.8 % of the theoretical amount of 650 g; 0.9 x 722).

c) 430 g (0.6 mol) of the phosphonamide described above, 300 ml of water and 300 g of isopropanol are placed in a 2 liter four-necked flask equipped with clamping devices for a slight excess pressure. Then 40 g of 85% phosphoric acid are added dropwise to the mixture in order to adjust the pH to 3.0 to 3.5. 28 g of ethylene oxide are introduced into the mixture with stirring at 50 to 60 ^{° C. and while flushing with nitrogen.} A total of 24.0 g is absorbed.

The mixture obtained is then ^{treated at a bath temperature of HO 0} C under a line vacuum and then filtered. The weight of the end product is 437 g

Analysis: Found: N »3» 0%

Calculated: N ■ 3.3

. the end product has the formula

CH

3
3

H ₂ PO ₄

d) Since the product of the cake ατ »1 was I * 1.25 % γ solution in a solution *! ttel # e * l # * J |, from 520 ml KeOH and 1000 al OCl ₄ . insisted on jylon Faille and Dacron according to the AATCG standard test method 76 * 1959

The swatches were conditioned for 24 hours "at 22 ° C and a relative humidity of 50 % and the speäifi-

-9-

0 09816/1891 ^r ■ "

ORIGINAL BATHROOM

Sheet 9 -

see resistance measured. The following results were obtained:

Log ohms / square cm, Kylon-Faille Dacron

untreated samples

treated with Piiospiionauid

Example 2:

14.02
8.79

13.46 8.65.

The Pliojpiionaraid was described as in Example 1 under (a) and (b) Höi-gea bell 'ü *

c) In a 2-liter ~ ^tr ierhalskolben, the light Cterdeuck gogsn with closing clips is equipped, are 430 g (0, ö koi) of ohiJii baechriebenen phosphonamide, 300 ml of water 300 g UIID iaopropanoL added. About the pH of the mixture. a, .f 3.0 bLj 3.5 airivstellen, adds 108 g 1/1 H ₉ O / chö ^ isch pure. ¹ HIiD. Za of this mixture are stirred • and. Scickstofr3;) äLvrur; at 50 to 60 ° 0 29 g of ethylene oxide (from e ^ ne ^. cylinder) ^. ^ eoen. Of this, 22.5 g are absorbed.

Z ^ i L -lialtene product is kept at H ⁰ O bath temperature under LviirMncsvakuum and then filtered. The weight of the end product is 451 g.

Analysis: Found: Nitrogen - 4.8 % Calculated: 5> O7 % The oxide product has the formula:

-ι +

ti-CH

CH ₂ -CH ₂ -OH _-

009816/1891

-10-

BATH ORIGINAL

-Sheet 10- ¹⁹⁴⁸² OI

d) The quaternary compound formed is in a HeOH / CCl. (520 ml / 1000 ml) -solvent mixture on Dacron and B wool samples at an application rate of 1.25 % ea ha ore. -Shirt of AATGC Standard Test Method 76-1959 applied.

The fabric samples are conditioned at 22 ° C and 50 % relative humidity for 24 hours and the specific resistance is measured. The following results are obtained:

^! treated sample

raic phosphonamide treated Swatch

L. or ohms / square , 46 cotton 24 Dacron , 96 14, 87 13th 8th, 8th

The product was as in Example 1 under (a) and (b) "hes Dan made.

c) In a two-liter four-necked flask equipped with a closure. ": ^.;, in a blessing slight overpressure, put 430 pounds (0.6 mol) of the carbamate described above, 300 ml of wanner and 300 ml g of isopropanol are added. In order to adjust the pH of the mixture to 2.0 to 5.3, 47.5 g of H ^ SO ^ are added. The mixture is ^{stirred at 50 to 60 °} C. and flushed with N ^. ethylene oxide (30.0 g of a cylinder) is added. a total of 2S g Ithylenoxyd be absorbed by the mixture.

The product is then kept at a bath temperature of 110 ° C. under a vacuum and then filtered. The weight of the llid product is 440 g »

Analysis: Found \ £ -tioketoff »3»! % Calculated: ^'i; C «

The end product best «at the formula: BAD ORfGIMAL

-11-009818 / 1891

- sheet 11 -

^CH 3 ^(CH 2 ⁾ 12-15 ^(CH 2 ^CKO) 1.85

■ ir

η +

NHCH ₀ CH ₀ CH-N-CH 2 2 2 ι J

CH-CH-OH 2 2

HSO ₁

d) The compound formed was from MeOH / CCl (520 ml / 1000 ml)

-ot

Mixing on nylon faille and polypropylene swatches applied at an application rate of 1.25% according to AATCC Standard Test Method 76-1959.

The brine samples were conditioned at 22 ° 0 and 50 % relative humidity for 2 · + 3 "c - Jews and the specific resistance was gc-eM ^ en. The following results were obtained:

Log ohms / square cm.

Nylon faille Polypropylene unlisted sample 14.02 14.64 treated with phosphonamide
Fabric sample 8.85 9.10 Be. " Srlal 4:

u. Ia a round bottom flask are added 306 weight parts (4.0 Get EO) s ..c egg Athoiiylats of Octylalkohele. Under stirring, to the ethoxylate with about 20 to 30 ⁰ C within 1.5 "bie 2 hours 77 parts (0.5 milliliters) Phospaoroaychlorid. Thereafter heated"#n the mixture to 60 bii 70 ⁰ C and keep it " ine hour XEJ | g at this temperature After "entniiaat at a · · Erob and repeatedly dae Probenehaen at intervals of an" hour until the chlorine content in the sample hydrolyaierten as low as is theoretiech aöglich..

b) In a flask equipped with a stirrer, two dropping funnels,

009816/1891

BATH

- sheet 12 -

If a thermometer and PE meter are fitted, 500 ml of water and 91 S (0.9 KoI) of dimethyl propylenediamine are added. 623 g (0.9 mol) of the phosphonaside prepared according to (a) and 30% i \ aCx *. A total of 108 g of 30% Έ ^ ΟΞ are required for this. After all the reaction participants have been added, the mixture is stirred for 15 minutes at room temperature and then adjusted to pH 9.0 with HGL. A total of 13 »0 g is required. The product obtained is then freed from water at 40 mm pressure and the residue is filtered. The yield is 525 g = 80.9 %. The theoretically possible yield is 0.9 x 758 = 682 g. -

c) 455 g (0.6 mol) of the above-mentioned phosphonamide, 350 ecm of water and 45 g of EUPO ^ are placed in a 1 liter four-necked flask with pressure locks against a slight excess pressure, whereby the pH of the mixture is between 3 * 0 to 3) 5 lies. The mixture is then ^{stirred at 50 to 60 0} G and rinsed with I ^. Ethylene oxide (33 g from a cylinder) is added. A total of 26 g of ethylene oxide are absorbed by the mixture.

The product is at 110 ° C bath temperature in a line vacuum treat and then filtered. The weight of the final product tete-iSu 460 g.

Analysis: Found: Nitrogen »2.9 % Calculated: 3.1 %. The product has the formula:

CH ₃ (CH ₂ J ₇ (CH ₂ CHO) ₄

Il

—P—

NHCH ₂ CH ₂ CH ₂

.N-CH

CH -CH OH 2 2

-13-

009816/1891

BATH

- sheet 13 -

d) The compound formed is in a 2.5% solvent mixture (52, ο ml MeOH and 1000 ml COl ^) on Dacron and nylon paille swatches conforming to the AATGG standard Test method 76-1959 applied.

The fabric samples are conditioned for 24 hours at 22 ° C and 50 % relative humidity and the specific resistance is revealed. 2s the following results are obtained:

Log 0hm / Q, square cm, Dacron Kylon-ffaille

unbeii £ Jidsl "c; e sample

treated with phosphonamide

Swatch

13.46
8.92

14.02 9.08

jjkJU- cS Z ' - * - 3-i. pi

a) 660 parts by weight of nonylphenol ethoxylate (10.0 mol 10) are placed in a round bottom flask. The A'thoxylat is stirred at 20 to 50 ⁰ C, and to 77 parts (0.5 mole) of phosphorus oxychloride are added dropwise within 1.5 to 2 hours. Thereafter, the mixture is heated to 60 to 70 ⁰ C and keeps it bsi this temperature for one hour. Then dry nitrogen is passed through the mixture and kept at the same temperature for one hour. After that, samples are taken from the mixture at one hour intervals until the hydrolyzed sample has such a low chlorine content that

w ^ 3 ύ-c is theoretically possible.

b) In a flask equipped with a stirrer, two dropping funnels, thermometer and a pH measuring device, 700 ecm V / water and 91 g (0.9 mol) dirnethylpropylenediamine are added. to the mixture is added while stirring at room temperature within 1 to 1.5 hours at the same time 1260 g (0.9 mol) Chlorophosphonate and JO% sodium hydroxide solution at such a rate, that the pH is between 10.5 and 11.0.

009816/18 91

-14-

BATH

- sheet 14 -

A total of 150 g of 30% ITaOH are required. After the reactants have been added, the mixture is stirred for a further 15 minutes at room temperature and then adjusted to pH 9.0 using HGL. 12.0 g are required for this. The product obtained., ·. is then freed from water in vacuo at 40 mm pressure and filtered. The yield is 1053 g = 79.8 % (theoretical yield = 0.9 1466 = 1320 g).

c) 880 g (0.6 mol) of the above-mentioned phosphonamide, 400 ecm of water and 400 g of isopropanol are placed in a 2 liter four-necked flask equipped with pressure closures for a slight excess pressure. Thereafter, v / ground 40 g of 85% phosphoric acid was added, "set to 3 * 5. Subsequently the mixture is at 50" to adjust the pH value to 3 »0 stirred until 6O ⁰ C and purged with lip. Then 28 g of ethylene oxide are added from a cylinder. A total of 24.0 g of ethylene oxide are absorbed by the mixture.

The product obtained is ^{treated at HO 0} G bath temperature in a line vacuum and then filtered. The weight of the end product is 886 g.

Analysis: Found nitrogen »1.55 % Calculated: 1.74 %. The product has the formula:

CK ₃ (CH ₂ ) ₈ (CH ₂ CHO) ₁₀

η +

NHCH ₂ CH ₂ CH ₂ N-CH ₃

^CH 2 ^CH 2 ^OH -i

H ₂ PO,

d) The compound formed is in a solvent mixture (520 ml MeOH, 1000 ml GGl ^) "on polypropylene and Dacron fabric

BATH ORIGINAL

-15-

009816/1891

- sheet 15 - '

samples applied in an application amount of 1.25% according to the AATOC standard test method 76-1959.

The fabric samples are "conditioned" at 22 ⁰ O and 50 % relative humidity for 24 hours and the specific resistance is measured. The following results are obtained for 2 seconds:

Log ohms / square cm Polypropylene Dacron

untreated sample 14.64 13.46

treated with phosphonamide

Swatch 8.98 8.74 λ

Example 6.

a) 288 parts by weight of an ethoxylate (1.85 mol - ^ C) of a straight-chain primary Cj ^ -C-jc alcohol mixture, which has an average molecular weight of 209 and consists of 5% C ₁₁ , 25 % C _{12, are placed in a round bottom flask} , 30 % C ₁₃ , 30 % C ₁ ^ and 10 ^c / o C ₁ C is composed. To the ethoxyate are under

Stirring at a temperature of 20 to 30 ° C. for 1.5 hours, 153 parts (1.0 mol) of phosphorus oxychloride are added, the mixture is then reduced to 60 to 70 ° C. and kept at that temperature for an hour. Thereafter, dry ß-CICL:.. 3-jo * f passed through the mixture and held "LcxiZ ~ ^oe i- & ^er specified temperature for a further one hour after a sample is taken and analyzed, the sampling and analysis at intervals of one hour continued until the chlorine content of the hydrolyzed sample is so low that v / io KiS is theoretically possible.

b) In a flask equipped with a stirrer, two dropping funnels, C-her- ^ ometer and a pH meter ^ 00 ecm V / water and 182 g (1.8 mol) dimethylpropylenediamine everyone is practicing. This is added while stirring at room temperature within from 1 to 1.5 hours at the same time 364 g (0.9 mol) that

00 9 816/1891 ~ ¹⁶ ~

BAD ORiGSNAL

- sheet 16 -

Chlorophosphonate and 30% NaOH prepared according to (a) at such a rate that the pH is kept between 10.5 and 11.0. A total of 230 g of 30% NaOH are required. After adding the sodium hydroxide solution, the mixture is stirred for 15 minutes at room temperature and then adjusted to pH 9.0 with chemically pure HGl. A total of 22.0 g is required. The water is then drawn off from the product at a pressure of 40 mm and the residue is filtered. The yield is 402 g, ie 83 »3 %. The theoretically possible yield is 0 * 9 x 536 = 482 g.

c) 322 g (0.6 mol) of the phosphonamide described above, 200 ecm of water and 200 g of isopropanol are placed in a 1 liter four-necked flask with locking clips against a slight excess pressure. Are added to the mixture, 45 g of 85% phosphoric acid, whereby the pH value is adjusted to 3> 0 "to 3i5 After rührx;. The mixture at 50 to 6Q ⁰ O under Np-flushing and outputs to a cylinder 54 - g of ethylene oxide. 47.0 g of ethylene oxide are absorbed by the mixture.

The product is then in line vacuum at bath temperature treated at 110 ° C and then filtered. The weight of the end product is 470 g.

Analysis: Found nitrogen = 6.71 % Calculated ■■ - 6.85%. The product has the! Formula

CH. (CH ₂ J _12-1 5 (CH ₂ CHO) _{1 #}

Il

-P-

NHCH ₂ CH ₂ CH ₂ N-CH ₃

CH ₂ CH ₂ OH

d) The compound ^{J formed} was dissolved in a 1.25% solvent mixture consisting of 520 ml of MeOH and 1000 ml of OCl ^

0 0 9 816/1891

-17-

- Sheet I? -

on cotton and dacron fabric samples according to the AATCC standard test method 76-1959 applied.

The fabric samples were conditioned at 22 ^° C. and 50% relative humidity for 24 hours and the specific resistance was measured. The following results were obtained:

Log; Ohm / square cm cotton dacron

untreated sample

swatch treated with phosphonamide

14.24
8.68

13.46 8.73

-le-Z patent claims:

0 09816/1891

Claims (1)

- sheet 18 - Patent claims 1.) Antistatic phosphorus compound of the formula RO (CH ₂ .CHO) X NH-CH ₂ CH ₂ CH ₂ -N Y ^ in which S is an alkyl or alkaryl radical with at least Carbon atoms, X is hydrogen or a methyl or ethyl radical, R ^ and I ^ alkyl or hydro ^ alkyl radicals with 1 to 3 carbon atoms, R-, a hydroxyalkyl radical with 1 to 4 carbon atoms, Y is an anion, m is an integer from 1 to 10, η 1 or 2 and ρ 1 or and the sum η + ρ = 3. 2.) Antistatic phosphorus compound of the formula: (CH ₂ J _12-1 Ii —P_ CH. NHCH ₂ CH ₂ CH ₂ N-CH ₃ CH ₂ -CH ₂ -OH H ₂ PO ₄ 5 ·) "Antistatic phosphorus compound of the formula: —P— NHCH C H CH gh J 2 009816/189 1 NO. -19- -Sheet 19 - 4.) Antistatic phosphorus compound of the formula :. ^CK 3 ^{(CH 2>} 12-l _£ i ^CH 2 ^CHO> ₁ .8 ₅ —Ρ— NHCH_CH-CH _O N —CH * λ 2 ι 5.) Antistatic phosphorus compound of the formula j CH ₃ (CH ₂ J ₇ (CH ₂ CHO) ₄ Ii -ρ- J 2 NKCH ₂ CH ₂ CH ₂ N-CH ₃ CH ₂ CH ₂ OH 6.) Antistatic phosphorus compound of the formula: Il -P- NHCH ₂ CH ₂ CH ₂ / ^CH 3 H-CH, CH ₂ CH ₂ OH 7.) Antistatic phosphorus compound of the formula: O ·
Il "NBOH ₂ CH ₂ CH ₂ N ^ H ³ " —Ρ— ι ³ CH ₂ CH ₂ OH τ + J 8.) Methods of reducing static electricity generated by natural or synthetic fibers, 009816/1891 -20- - sheet 20 - characterized in that one pasers with connections the formula, RO (CH ₂ -CIiO) ra -i 11 s ^r A Ii I / NH-CH ₂ CH ₂ CK ₂ -NR ₂ R. - ¹ p overlooks, in which 3 is an alkyl or alkaryl radical with at least 7 carbon atoms, X is hydrogen or a Ks-Jiiyl- or Ä'thylrest, E ₁ and Rp are alkyl or hydroxyalkyl radicals with 1 to 3 carbon atoms, IU is a hydroxyalkyl radical with 1 to 4 carbon atoms, T an anion, ei an integer from 1 to 10, η the number 1 or 2, '- p the number 1 or 2 and the sum of η + ρ = 3 is o. BATH ORIGINAL 0098 16/189 1