DE1768060A1 - Substituted carbamates as antistatic substances and processes for their production - Google Patents

Description

The present invention relates to new and useful compounds which are based on synthetic and natural fibers applied, act as antistatic substances, e.g. polyester fibers, acetate silk, wool, polyolefins and the like, and processes for their manufacture. In particular, the present invention relates to substituted carbamates, which exhibit antistatic properties and which result from condensation of alkyl and aryl polyalkylene oxycarbamates with a substituted alkyl diamine and subsequent acidification and alkoxylation arise.

109838/1748

The commercial importance of the synthetic fiber industry has underlined the importance of antistatic substances and finishes, since synthetic fibers, e.g. Polyester fibers, acrylic derivatives, vinyl compounds, etc., known to be a generator of static electricity. While other fibers, e.g. wool or viscose, under normal Humidity conditions generate static electricity only to a small extent and other fibers, such as acetate, Rayon and wool are only moderated producers who only require a few precautionary measures in the processing process, e.g. controlled humidity, the processing of synthetic fibers, like the one listed above, is to make the build more static Preventing electricity is not easy.

While many, non-durable finishes with a massive effect against the build-up of a static field in synthetic fibers are few and complete known satisfactory, durable antistatic agents. Most of the finishes designed to prevent static build-up Electricity used in synthetic fibers belong to the category of surfactants, although there is no marked similarity with no relationship between surface activity and antistatic effectiveness.

In general, antistatic substances act in two ways, both of which improve the electrical conductivity of the fiber surface. Antistatic substances are either themselves good conductors of electricity or they are hygro- 109838/1748

ekopisoh and concentrate the atmospheric moisture from the fiber.

Most of the antistatic substances fall into one of the three following groups »(1) nonionic polyhydroxy and polyethyleneoxy compounds; (2) cationic or neutral Nitrogen compounds with a hydrophobic bond; (3) long-chain phosphates, phosphonates or other building materials ige phosphorus compounds. Other groups include sulfonated oils, ester emulsions and other fiber additives, which are based on the antistatic effect of the emulsifying agents.

Long-chain, quaternary ammonium salts show a pronounced antistatic effect and are widely used in this field. The quaternary compounds are in antistatic Finishes are often encountered; they are often combined with other aids that are themselves antistatic may or they serve the second purpose of binding the finish to the fiber. The water-insoluble salts of higher amines have also been used in conjunction with polystyrene sulfonates as nylon antistatic agents.

In accordance with the present invention, it has been found that certain compounds having a carbamate structureT · Ib SSr '^; * have kUl, especially those that are derived from the chlorocarbv ^ mt a "primary or secondary alkoxylate

109838/1748

- sheet 4 -

alcohols or an alkylphenol and a dialkylaminopropylamine derive, show excellent antistatic properties on the synthetic fiber. These novel carbamates not only convey the antistatic activity associated with the amide bond and the quaternary configuration, but also the desired antistatic properties of a polyalkoxylated hydrophobic compound. Unexpectedly a potentiation occurs through the combination of these chemical punctures in the molecular structure of the carbamate, that does not apply to the simple mixing together of antistatic compounds of the nonionic and the amide type are watching.

The antistatic agents according to the invention correspond to the following general formula:

O Q RO (CHjCHO> - - C -NHCHjCHjCHj

Y -

where R is an alkyl radical or an alkaryl radical with at least 7 carbon atoms, X is a hydrogen atom, a methyl radical or an alkyl radical, η is an integer between 1 and 10, R and R ₂ are alkyl or hydroxyalkyl radicals with 1 to 3 carbon atoms , R, is a hydroxyalkyl radical with

1098'3 8/1748

1 to 4 carbon atoms and Y is an anion.

Examples of alkyl or alkaryl radicals for R are i Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Hexadecyl, octadecyl, nonadecyl, fiicosyl, docosyl, pentacosyl etc., methylphenyl, ethylphenyl, butylphenyl, hexylphenyl, Octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, Pentadecylphenyl, Octadecylphenyl, Nonadecylphenyl, etc.

Examples of alkyl and hydroxyalkyl radicals for R, and R_ are:

Methyl, ethyl, propyl, isopropyl, hydroxymethyl, hydroxyethyl, Hydroxypropyl, dihydroxypropyl, etc.

Examples of hydroxyalkyl radicals for R 1 are; Hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, D! Hydroxypropyl, dihydroxybutyl, etc.

Examples of anions for Y are:

Halides, chloride, bromide, iodide, phosphates, nitrates, sulfates and the like.

The compounds of the invention are obtained by condensation of an alkyl or alkaryl polyalkylene oxychlorocarbonate with a substituted alkyl diamine with subsequent acidification and alkoxylation.

The alkyl or alkaryl polyalkylene oxychlorocarbonate is produced by the reaction of phosgene with a polyalkylene oxylated ali-

109838/1748

Phatic alcohol or alkylphenol obtained according to the following reaction scheme under normal conditions:

RO (CH ₂ CHO * -H + COCl »RO (CH ₂ CH-O) ^ COCl + HClT

In general, the same quantities of reactants are used, so long phosgene gas passes under the surface of the polyalkyleneoxylated, aliphatic alcohol or Alkylphenols β ir until all hydroxyl groups are formed Chlorocarbonate are consumed as verified by infrared analysis or other suitable methods.

The polyalkyleneoxylated aliphatic alcohol or the Alkylphenol is obtained by any conventional method using 1 to 10 moles of alkylene oxide, e.g., ethylene oxide, Propylene oxide or butylene oxide, per mole of the aliphatic alcohol or alkyl phenol. That with reaction I formed alkyl or alkaryl polyalkylene oxychlorocarbonate is used with the same amount of gamma-dialkyl- or dialkanolaminopropylamine according to the following reaction scheme displaced »

109838/1748

- sheet 7 -

11

RO (CB ₂ CBOt _n COCl + HNCH ₂ CH ₂ CH ₂ N

RO (CH ₂ CHO) _n X

-CONBCH ₂ CH ₂ CH ₂ N

The substituted amide formed in reaction II is through an alkylene oxide or a hydroxylated alkylene oxide in the presence an inorganic acid into the quaternary compound convicted. Such a reaction proceeds as follows:

R.

HOKCONHCHjCHjCHj N + »lkyltnt oxidt *. ^R 2

ROtCH ₂ CH ₂ O) _n -CONHCH ₂ CH ₂ CH ₂ N I

Reaction III should better be broken down into two partial reactions:

IHa

RO (CH ₂ CHO ^ COHBCH ₂ CH ₂ Ch ₂ N

+ HY

RO (CH ₂ CBOf

(CH ₂

x 109838/1748

γ -

- sheet 8 -

and

R ₂

γ "* + alkylene oxide

RO (CH ₂ CHOf ₀ - CONHCH ₂ CH ₂ CH ₂ N

In reactions I, II, III, Ilia and IIIb have R, R-,, X, Y and η have the meaning given above.

In the preferred synthesis, a commercial mixture of straight-chain, aliphatic alcohols of the approximate composition 5 # C ₁₁ , 25% C ₁₂ , 30% Cj *, 30% C ₁₄ and 10 $ C ₁₅ using an alkaline catalyst at 120 to 150 ^° C and treated from 0 to 1 atm with alkylene oxide until one to ten moles of oxide are absorbed. Instead of the alkaline catalyst, acidic catalysts such as BF ,, ELPO are also used. and the like. Secondary alcohols, w £ e 2-decanol, 3-decanol, 4-decanol, 3-Dodecanpl, 4-tetradecanol, 6-hexadecanol and the like, or a mixture thereof, as well as alkyl phenols, such as octylphenol, linear decylphenol, branched Sodecylphenol, etc., can be substituted for the primary aliphatic alcohol. The

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176806Q

- sheet 9 -

Standing alkyl or alkaryl polyalkyleneoxyalkanol is then treated with phosgene to form the corresponding alkyl or alkaryl polyalkylene oxychlorocarbonate, the latter is converted into its carbamate with gamma-dialkylaminopropylamine. The carbamate is acidified and with an alkylene oxide converted to the quaternary ammonium salt.

The antistatic substances according to the invention show unexpectedly advanced antistatic properties, mainly in application to synthetic fibers such as Polyesters, aerials, polyolefins, polyamides, etc. Such antistatic substances can lower the electrical charge below a potential of 3 kilovolts and for one maintain such a potential for a longer period of time.

The following specific examples are intended to illustrate the invention Explain substances and the process in more detail.

Example 1:

a) 288 parts by weight of the ethoxylate (about 2 mol ethoxylate) of the C ₁₂ -C .. (- mixtures of straight-chain primary alcohols, average molecular weight 209 with the composition 5% O ₁₁ , 25 # O ₁₂ , 30% C ₁₅ , 30% C ₁₄ and 10 $ O _15. The ethoxylate was stirred at room temperature (20 ° -30 ° C.) and phosgene was passed under the surface over 1.5 to 2 hours

109838/174 8

continued until the absorption of the hydroxyl groups completely disappeared when examined by infrared spectrography. For this purpose, a total of 109 g of phosgene (1.1 mol) needed.

b) 500 ml of water and 91 g of dimethylpropylenediamine (0.9 mol) were placed in a beaker with a stirrer, two dropping funnels, thermometer and pH meter. You mixture was at Stirred room temperature and within 1 to 1.5 hours 316 g (0.9 mol) of the chlorocarbonate prepared according to a) and 30 # sodium hydroxide solution added dropwise at the same time in such an amount that that the pH adjusted between 10.0 and 10.5. A total of 141 g of 30% sodium hydroxide solution were required for this. After complete addition was stirred for 15 minutes at room temperature and then the pH value with concentrated, pure Hydrochloric acid brought to 9.0. About 2.0 g of hydrochloric acid was used for this. The water was drawn off at 40 mm of mercury and the residue was filtered. The yield was 293 g.

c) 250 g (0.6 mol) of the carbamate from b), 250 ml of water and 104 g of concentrated, pure hydrochloric acid were placed in a 1 liter 4-neck flask with secured ground-joint connections for light pressure and the pH was adjusted to 3 to 3.5 set. The mixture was stirred at 50 to 60 ^° C. and purified with nitrogen. 26 g of ethylene oxide was added from a cylinder, 19.0 g of which was absorbed.

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The product was stripped off under vacuum at RO and filtered.

Weight of the end product 187 g.

$> Nitrogen: found = 4.9; calculated = 5.6.

The product corresponds to the formula:

C _12-15 O

CH ₂

COMBCH ₂ CH ₂ CH ₂ N-CH ₂

^ CH ₂ CH ₂ OH

d) The quaternary salt formed as described above was from the solvent mixture MeOH / CCl. (520 ml / 1000 ml) on polypropylene and Dacron fabric pieces in 1, 25 # concentration according to IATCC Standard Test Method 76-1959 applied.

The specimens were ⁰ C and 50 $> relative humidity for at least 24 hours at 22.2 and then genessen the resistivity. The following results were obtained:

log ohms / square polypropylene dacron

Control 14.64 13.26

quaternary carbamate 7.77 7.65

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- sheet 12 -

Example 2:

Parts a) and b) are the same as in example

c) 250 g (0.6 mol) of carbamate, 250 ml of water and 108 g of water / concentrated pure nitric acid (1: 1) were placed in a 1 liter 4-neck flask with a ground joint for light pressure and the pH was adjusted to 3 , Brought 0 to 3.5. The mixture was stirred at 50 to 60 ⁰ C and bubbled with nitrogen. Then 36 g of ethylene oxide were fed from a cylinder, 19.5 g of which were absorbed in total.

The product was stripped off at 110 ° under vacuum and filtered.

The yield was 242 g.
i> nitrogen ι found - 7.2 \ wrtohnet ■ 8.0.

The product corresponds to the formula:

^C 12 ** 15

CH,

CH ₂ CH ₂ OH

MO.

d) The quaternary salt described above was applied from the solvent mixture methanol / carbon tetrachloride (520 ml / 1000 ml) to Dacron and cotton fabric pieces in a concentration of 1.25, according to AATCO Standard Test Method 76-1959.

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- sheet 13 -

The pieces were conditioned for at least 24 hours at 22.2 ° C and 50 % relative humidity and then the resistivity was measured. The following results were obtained:

log ohms / square

Carbamate Dacron cotton control 13.26 14.24 quaternary 7.59 7.90 Example 3:

Parts a) and b) are the same as in Example 1.

c) 250 g (0.6 mol) of carbamate, 250 ml of water and 47.5 g of phosphoric acid were placed in a 1 liter four-necked flask with a safety ground joint, the pH being between 3.0 and 3.5. The mixture was stirred at 50 to 60 ⁰ C and sparged with nitrogen. Then 36.5 g of ethylene oxide were fed from a cylinder, of which a total of 24.0 g would be absorbed.

The product was drawn off at HO ⁰ C under vacuum and filtered.

The weight of the final product was 147 g.

i » nitrogen: found = 4.8; calculated = 5.0.

The product corresponds to the following formula:

109838/1748

CH ₃

CH ₂ CH ₂ OH

H ₂ PO ₄

-Sheet 14 -

176806 Q

d) The previously described quaternary salt was made from the Methanol / carbon tetrachloride solvent mixture (520 ml / 1000 ml) on nylon and polypropylene cloth pieces in 1.25 # concentration according to AATCC standard test Method 76-1959.

The pieces were conditioned for at least 24 hours at 22.2 ⁰ C and 50 i "relative humidity and then measured the resistivity. The following results were obtained:

log ohms / square

Carbamate Si lon Polypropylene control 13th , 91 14.64 quaternary 7th , 85 7.80 Example 4:

a) A round flask was charged with 174 parts by weight of an ethoxylate (1.0 mol ethoxylate) of octyl alcohol. The ethoxylate was stirred at Conversely Bunge temperature (20 to 30 ⁰ C) and phosgene directed 1.5 to 2 hours under the surface. The addition of phosgene was continued until the complete elimination of the hydroxyl groups was shown in the infrared spectrogram. A total of 107 g (1.08 mol) of phosgene was consumed.

b) In a beaker equipped with a stirrer, two dropping funnels, 300 ml of water and 91 g of dimethyl propylenediamine (0.9 mol) were added to the thermometer and pH meter. The mix was

109838/1748

- sheet 15 -

stirred at room temperature and 213 g of chlorocarbonate (0.9 mol) prepared according to a), and 30 # sodium hydroxide solution were added dropwise over 1.5 to 2 hours at a rate that the pH remains between 10.0 and 10.5. A total of 38 g of 30 # sodium hydroxide solution were required. After adding all of the reactants, it was now. The mixture was stirred for 15 minutes at room temperature and the pH was then brought to 9 »0 with concentrated pure hydrochloric acid. A total of 3.0 ml hydrochloric acid were required for this. The water was drawn off at 4-0 mm pressure and the. Filtered residue. The yield was 218 g, the theoretical yield 0.9 303-272 g, that is to say the percentage yield 80.2%.

c) 182 g (0.6 mol) of the above carbamate, 175 ml of water and 45 g of H *** ⁰ , to adjust the pH to 3.0 to 3.5 given. The mixture was stirred at 50 to 6O ⁰ C and sparged with nitrogen. 33 g of ethylene oxide was fed from a cylinder and a total of 21 g was absorbed therefrom.

The product was drawn off at HO ⁰ C under vacuum and filtered. .

The yield was 190 g.

i » nitrogen: found = 5» 9 ϊ calculated β 6.3.

The product corresponds to the formula

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- sheet 16 -

C ₈ H ₁₇ O (CH ₂ CH ₂ OKCOHHCH ₂ CH ₂ Ch ₂ N

CH.

CHi

CH CH OH

d) The quaternary salt described above was obtained from the solvent mixture methanol / carbon tetrachloride (520 ml / 1000 ml) on Daoron and nylon fabric pieces in 2.5 # Lger Concentration applied, according to AATCC Standard Test Method 76-1959.

ο The pieces have been left at 22.2 C and for at least 24 hours 50 % relative humidity and then measured the specific resistance. The following results were obtained

log 0hm / square Dacron nylon

Control 13.26 13.91

quaternary carbamate 8.92 9.14

Example 5;

a) Sin Sund flask was charged with 660 parts by weight of an ethoxylate (10.0 mol ethoxylate) of nonylphenol. The ethoxylate was stirred at ambient temperature (20-30 ⁰ C) and phosgene introduced 1.5 to 2 hours under the surface. The addition of phosgene was continued until the complete removal of the hydroxyl groups was shown in the infrared spectrogram.

109838/1748

A total of 112 g of phosgene (1.15 mol) were consumed.

b) In a beaker equipped with a stirrer, two dropping funnels, The thermometer and pH meter were 1100 ml of water and 91 g of dimethyl propylenediamine. (0.9 mol) given. The mix was stirred at room temperature and 650 g of chlorocarbonate (0.9 mol) prepared according to a), and 30 # strength sodium hydroxide solution for 1.5 to 2 hours at the same time at such a speed drops that the pH was between 10.0 and 10.5. A total of 150 g of 30% sodium hydroxide solution were required. After adding everyone The reaction partner was stirred for a further 15 minutes at room temperature and then the pH value with concentrated pure hydrochloric acid brought to 9.0. A total of 5.0 g of hydrochloric acid was required. The water was drawn off at 40 mm pressure and the Filtered residue. The yield was 596 g, the theoretical The yield was 0.9 789-710 g, so the percentage yield was 84.0. °

c) 475 g (0.6 mol) of dee carbamate, 45.0 ml of H ₂ O and 99 g of concentrated pure hydrochloric acid were placed in a 1 liter four-necked flask with a safety ground joint for light pressure, the pH being between 3.0 and 3 , 5 a. The mixture was stirred at 50 to 60 ⁰ C and sparged with nitrogen. 30 g of ethylene oxide was fed from a cylinder, of which a total of 22 g was absorbed.

The product was drawn off at 11O ⁰ C under vacuum and

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filtered. The weight of the final product was 495 g.

Nitrogen 2 found = 2.9; calculated «3.22.

The product corresponded to the following formula

Cl

d) The quaternary salt described above was applied from the solvent mixture methanol / carbon tetrachloride (520 el / 1000 ml) to polypropylene and Orion fabric pieces in a concentration of 1.25 #, according to AAICO Standard Teat Method 76-1959.

The pieces were conditioned for at least 24 hours at 22.2 ⁰ C and 50 i * relative humidity and then measured the resistivity.

The following results were obtained

log 0hm / square

Carbamate PolyDroüvlen 9 pounds ion control 14.64 14th • 24 quaternary 9.93 9 , 86 Example 6ι

By weighing 1.25 and 2.50 g of the antistatic »in

109838/1748

tared, 100 g WMSC bottles were. Baths prepared. That Solvent (520 ml methanol / 1000 ml carbon tetrachloride) is added in volume, i.e. 99 or 97 ml or in clear solutions were found in each case.

Pre-weighed and conditioned pieces of tissue (11 χ 12 cm) were placed in the appropriate baths and well for an hour

emotional. The movement consisted of a slight swing and twisting of the leg with the hand. The removed pieces of tissue were left Drain into the vessel for 10 seconds, fastened it on a hook with compensation and brought it to a 100% recording by gently pressing between filter paper.

All the pieces were comparatively easy on one Bring inclusion eu.

The finished pieces were kept in a steam-heated oven at 50 ^° C. overnight before conditioning.

After a conditioning of at least 40 hours at 50 i> relative humidity and 22.8 ⁰ C, the resistance of each fabric tückes front and rear transverse texture measured for tissue. From the average of the two; The measured values were calculated using the value log ohms / square, which is set out in the following table

-2o-109838/1748

- sheet 20 -

log ohms / square

Applied composition 1 * bath nylon Polypropylene Dacron
Type 54 Orion
(T-42) Product example I. 1.25
2.50 8.18
7.9o 7.77
7.43 7.65
7.45 8, Io
7.73 Product example II 1.25
2.50 8.15
7.69 7.84
7.62 7.59
7.41 7.9o Product example III 1.25
2.5o 7.85
7.75 7.8o
7.49 7.52
7.21 8, o5
7.62 Catanac * 1.25
2.50 7.49
8.33 8.56
8.27 7.16
7.99 8.19
8.27 control - 13.91 14.64 13.26 14.24

+ (registered trademark): commercially available antistatioum.

/ Claims:

109838/1748

Claims (9)

Claims 1.) Antistatic compound, characterized in that that they are of the formula RO (CHCHOi CNHCH ₂ CH ₂ CH ₂ N R. where R is an alkyl radical or an alkaryl radical having at least 7 carbon atoms; X denotes either a hydrogen atom, a methyl or ethyl radical,. η is a number between 1 and 10, R- and R ₂ stand for an alkyl or hydroxyalkyl radical with 1 to 3 carbon atoms, R is a hydroxyalkyl radical with 1 to 4 carbon atoms and Y is an anion. 2.) Antistatic compound, characterized in that it has the formula O C NHCH ₂ CH ₂ CH ₂ N ₂ CH ₂ ι · ■ ■ " CH, CH ₂ CH ₂ OH 109838/1748 is equivalent to. - Sheet 22 / Claims - 3.) Antistatic compound, characterized in that it has the formula CH. ^C 12-15? (CH ₂ CH ₂ Ot ₂ - ^ CNHCH ₂ CH ₂ CH ₂ N-CH ₃ CH ₂ CH ₂ OH is equivalent to. 4.) Antistatic compound, characterized in that it has the formula Il CH. NHCH ₂ CH ₂ CH ₂ N CH ₃ ^ CH ₂ CH ₂ OH H ₂ PO ₄ is equivalent to. 5.) Antistatic compound, characterized in that that they are of the formula CH. C ₈ H ₁₇ O (CH ₂ Ch ₂ O) -CNHCH ₂ CH ₂ CH ₂ N-CH CIL CH OH 109838/1748 H PO 2 4 is equivalent to. - Sheet 23 / Claims - 6.) Antistatic compound, characterized in that it has the formula CH ₄ CH ₃ \ ³ Cl is equivalent to. · (I. 7.) Process for the preparation of an antistatically active substituted carbamate, characterized in that a) Phosgene with a hydroxyl compound from the group of alkyleneoxylated derivatives of aliphatic alcohols and alkylphenols having at least 7 carbon atoms are treated, the corresponding Forms chlorocarbonate; b) that the product from a) is mixed with the same amount by weight of gamma-dialkylaminopropylamine M and that the corresponding carbamate is formed and c) that the product from b) with an alkylene oxide in the presence an inorganic acid, the corresponding quaternary ammonium salt being formed will. 8.) The method according to claim 7, characterized in that under a) so long phosgene gas under the surface of the Hydroxyl compound is passed until all in it 109838/1748 - Sheet 24 / claims »'768060 contained groups are converted into chlorocarbonate. 9.) The method according to claim 7, characterized in that the gamma-dialkylaminopropylamine dimethy! Propylenediamine and the alkylene oxide is ethylene oxide. 109838/1748