US3856895A

US3856895A - Phosphonamides

Info

Publication number: US3856895A
Application number: US00765001A
Authority: US
Inventors: L Schenck; J Beiswanger; F Eiseman
Original assignee: F Eiseman; L Schenck; J Beiswanger
Current assignee: Rhone Poulenc Surfactants and Specialties LP; Bayer CropScience Inc USA
Priority date: 1968-10-04
Filing date: 1968-10-04
Publication date: 1974-12-24
Anticipated expiration: 1991-12-24
Also published as: DE1948201A1; CH542885A; FR2019897A1; JPS4813533B1; GB1287915A; NL6915032A; CH514022A; BE739835A; CH1486269A4

Abstract

Phosphonamide antistatic agents having the formula :

WHEREIN R represents an alkyl phenyl, or alkyl-substituted phenyl radical having at least 7 carbon atoms, X represents hydrogen, methyl or ethyl, R1 and R2 are members of the group consisting of alkyl and hydroxy alkyl radicals of from 1-3 carbon atoms, R3 is a hydroxy alkyl radical of from 1-4 carbon atoms, Y is an anion, m is an integer of from 1-10, n is an integer of from 1-2, and p is an integer of from 1-2, and the sum of n + p 3.

Description

limited @ttes ll tet [1 1 Eiseman, .l r. et al.

[111 enemas [45] net. 242, 119741 PHOSPHUNAMIIDES ['76] Inventors: Fred S. Eiseman, In, 516 Summit--- Ave., Maplewood; Leslielvl.

Sehenck, 1558 Grouse Ln., Mountainside, both of N.J.; John P. G. Illeiswanger, 720 ColemanSL, I Easton, Pa.

22 Filed: (let. 4, 1196s [21] Appl. No: 765,001

[52] US. Cl 261N945, 117/138.5, 260/974,

' 260/984 [51] Int. (31. C(Wt 9/24 [58] Field of Search 260/945 [56] References Cited UNITED STATES PATENTS 2,302,805 11/1942 Schiissler 260/945 X OTHER PUBLICATIONS Kondratev et al., Index Chemicus, Vol. 19, page 57137(1965).

Primary ExaminerL0rraine A. Weinberger Assistant Examiner Richard L. Raymond Attorney, Agent, or FirmWalter C. Kehm; Samson B. Leavitt [57] ABSTRACT Phosphonamide antistatic agents having the formula wherein R represents an alkyl phenyl, or alkylsubstituted phenyl radical having at least 7 carbon atoms, X represents hydrogen, methyl or ethyl, R and R are members of the group consisting of alkyl and hydroxy alkyl radicals of from 17-3 carbon atoms, R is a hydroxy al-kyl radical of from l-4 carbon atoms, Y is an anion, m is an integer of from l-IO, n is an integer of from 1-2, and p is an integer of from 12, and the sum of n p 3.

7 Claims, N0 Drawings 11 PHOSPHUNAMIDES The instant invention relates to new and useful compositions of matter which function as antistatic agents when coated on-synthetic and natural fibers, e.g. polyester fibers, acetate rayons, wool, polyolefins, and the like, and to the method of use therefor. In particular. the instant invention is directed to substituted phos phonamides which exhibit antistatic properties, which phosphonamides'are prepared by the condensation of alkyl and aryl polyethyleneoxy chlorophosphonates with a substituted alkyl diamine, followed by acidifi cation and alkoxylation.

The commercial importance of the synethetic fiber industry has greatly emphasized the importance of anti static agents and finishes since synthetic fibers, e.g., polyester fibers, acrylics, vinyls, etc. are notorious static electricity generators. While other fibers, e.g.,

- cotton or viscose, do not generate the static electricity to any great extent under normal humidity conditions, and fibers such as acetate, rayon, and wool are only moderate generators, necessitating only some precautionary measures in the processing mill, e.g., a controlled high humidity, synthetic fibers such as mentioned above are not easily treated to control static electricity buildup.

While several non-durable finishes have been proposed which are moderately effective in eliminating static buildup on these synthetic fibers, few have been proposed which are completely satisfactory durable antistats. Most finishes employed to eliminate static buildup on synthetic fibers fall into the category of true surfactants although there is no really distinct similarity or correlation between surface activity and antistatic action.

In general, antistatic agents function in two ways, both of which improve the electrical conductivity of the fiber surface. Such antistatic agents are either reasonably good conductors of electricity themselves, or they are hygroscopic and help concentrate atmospheric moisture on the fibers.

The majority of antistatic agents fall into one of the following three categories: (I)' polyhydroxy and polyethyleneoxy non-ionic compounds; (2) cationic, or neutral nitrogenous compounds with a hydrophobic moiety in their structure; (3) long-chain phosphates, phosphonates, or other oxygenated phosphorus derivatives. Additional types include sulfonated oils and ester emulsions, and other fiber lubricant emulsions which depend on the particular emulsifying agent used for their antistatic effect.

Long-chain quaternary ammonium salts have a marked antistatic action and are widely used in this capacity. These quaternaries, in common with numerous antistatic finishes, are frequently used in combination with auxiliary agents which may themselves be antistats, or serve the secondary purpose of binding the finish to the fiber, as disclosed in U.S. Pat. No. 2,463,282. The water-insoluble salts of higher amines, together with polystyrene sulfonates, are described in U.S. Pat. No. 2,700,001 as nylon antistats. The use of phosphorus compounds in antistatic capacities is given in U.S. Pat. Nos. 2,575,382: 2,575,399, and 2,676,122. Hygroscopic salts, such as cyclohexylamine lactate, are disclosed in Ger. Pat. No. 840,694, while the use of polyethoxylated fatty acids and alcohols as antistatic agents for polypropylenes as well as fibers, is reported in U.S. Pat. No. 2,525,691.

In accordance with the instant invention, it has now been found that when one incorporates certain compounds which contain a phosphonamide structure within the molecule and, more specifically, those phosphonamidc compounds derived from chlorophosphonate of an alkoxylated primary or secondary alcohol or alkyl phenol and gamma-dialkylaminopropylamine, show excellent antistatic properties when applied to synthetic fibers. These novel phosphonamides impart not only antistatic properties associated with both an amide linkage and that imparted by a quaternary configuration but, in addition, they also impart the desirable properties and characteristics of polyethoxylated hydrophobes. Unexpectedly, the combination of these chemical functions within a phosphonamide molecular structure provides an enhancement lacking when one simply admixes antistatic agents of the nonionic and amide type.

It is, therefore, a principal object of the present invention to provide new and useful phosphonamide antistatic agents.

A further object of the present invention comprises the preparation of antistatic agents which have en-' hanced effectiveness with antistatic agents which contain an amide linkage and a polyalkoxylated hydr0- phobe.

Yet a further object of the instant invention is to prepare new and useful substituted phosphonamides which are derived from the chlorophosphonate of an alkoxylated primary or secondary alcohol or phenol and a substituted alkyl diamine.

Yet another object of the instant invention is to provide a process for the preparation of a new and useful antistatic agent, which processcomprises the condensation of alkyl and aryl polyethyleneoxy chlorophosphonates with a substituted alkyl diamine. followed by acidification and alkoxylation.

Still further objects of the instant invention will become more apparent from the following detailed description thereof.

The new and useful antistatic agents ofthe instant invention correspond to the general formula:

it R1 [RO o int mmm],1*-(N1I0mornorn-rvm X p wherein represents an alkyl phenyl or alkyl-substituted-phenyl radical containing at least 7 carbon atoms, X represents hydrogen, methyl orethyl, R, and R represent alkyl or hydroxy alkyl radicals having from 1-3 carbon atoms, R.-, is a hydroxy alkyl radical having from 1-4 carbon atoms. Y is an anion, m is an integer of from 1-10, 11 is an integer of from l2 and p is an integer of from l2. In particular, R may be exemplified, but is not limited to, the following alkyl, phenyl or alkaryl radicals:

heptyl octyl nonyl decyl undecyl dodecyl tridecyl hexadecyl octadecyl mcthylphcnyl cthylphenyl hutylphcnyl hexylphenyl octylphenyl nonylphenyl decylphenyl dodecylphenyl pentadecylphenyl octadecylphenyl nonadecylphenyl phenyl Exemplary alkyl and hydroxy alkyl radicals for R and R include:

methyl ethyl P py isopropyl hydroxymethyl hydroxyethyl hydroxypropyl dihydroxypropyl, etc.

Exemplary hydroxy alkyl radicals for R include:

hydroxymethyl hydroxyethyl hydroxypropyl hydroxybutyl dihydroxypropyl dihydroxybutyl, etc.

Exemplary anions for Z include:

halides chloride bromide iodide phosphates nitrates sulfates and the like.

In general, the novel phosphonamides of the instant invention are prepared by the condensation of alkyl and aryl polyethyleneoxy chlorophosphonates with a substituted alkyl diamine followed by acidification and alkoxylation. More specifically, in our preferred synthesis, a commercial straight chain aliphatic alcohol admixture comprising approximately 5% C 25% C 30% C 30% C and C is reacted with an alkylene oxide using an alkaline catalyst at ll50C. and l psig until one to ten moles of the oxide is added. In place of the alkaline catalyst, acidic catalysts such as BF H PO and the like can be used. Secondary alcohols such as 2 decanol, 3-decanol, 4'-decanol, 3- dodecanol, 4-tetradecanol, 6-hexadecanol, and the like or their admixtures as well as alkylphenols such as octylphenol, linear decyl phenol, branched dodecylphenol, etc, can be substituted for the primary aliphatic alcohol. The resultant alkyl or alkyl-arylpolyalkyleneoxyalkanol is then reacted with phosphorous oxychloride to form the corresponding mono or di alkyl or alkylarylpolyalkyleneoxy chlorophosphonate and the latter compound converted to its phosphonamide by reaction with gamma dialkylaminopropylamine. This latter derivative is acidified and reacted with an alkylene oxide to form its quaternary ammonium salt.

I The above process is in general in accordance with the following reactions:

ltOll ulkylulm oxirlu catalyst The novel substituted amide produced by reaction lIl can then be quaternized by reaction with an alkylene oxide or hydroxy substituted alkylene oxide in the presence of an acid. Such reaction may be represented as follows:

no oinciro o in l 1 ll x "P Nll(ClIz),\N

+ alkylcnuoxirlo NY in the above reactions R, R,, R R X, m, n, P, and Y are previously defined. A represents an integer of from 1 to 5.

The new and useful antistatic agents of the present invention have been found to have unexpectedly advantageous antistatic properties, particularly when applied to synthetic fibers, such as polyesters, acrylics, polyolefins, polyamides, etc. Such antistatic agents have been found to reduce and maintain the electrostatic charges for extended periods of time below a potential of 3 kilovolts.

The present invention will now be described by refer ence to the following specific examples. Such examples are presented for purposes of illustration only, and the present invention is in no way to be deemed as limited thereto.

EXAMPLE 1 a. To a round bottom flask was charged a total of 288 parts by weight of an ethoxylate (1.85 moles E0) of a C C straight chain primary alcohol admixture calculated as a 209 MW. average and having the compo- The ethoxylate was agitated at ambient temperature (2030C.) while 77 parts phosphorous oxychloride (0.5 mol.) were dropped in over about 1.5 to'2.0 hours. After addition of phosphorous oxychloride was completed the batch was heated to 60-70C. and held 1 hour. Dry nitrogen was then bubbled through the mixture and the temperature was maintained for one hour. Samples were then run and repeated at one hour intervals until the percent chlorine on hydrolyzed sample showed as low as theoretical.

b. To a beaker equipped with agitator, two dropping funnels, thermometer and a pH meter were charged 500 ml. water and 91 gms. dimethyl propylene diamine (0.9 mole). These materials were agitated at room temperature while 591 gms. of the chlorophosphonate (0.9 mol) prepared in (a) and 30% NaOH were dropped in simultaneously over about 1 to 1.5 hours at such a rate as to maintain the pH between l0.5 to 11.0. A total of 130 gms. 30% NaOH was required. After all reactants were added the batch was agitated 15 minutes at room temperature and then brought to pH 9.0 with CP HCl.

EXAMPLE n The product was prepared as in Parts (a) and (b) of Example I.

c. To a 2 liter 4 necked flask with joints clamped for slight pressure were charged 430 gms (0.6 mole) of the above phosphonamide. 300 ml H 0 and 300 gms isopropanol. Then 108 gms l/l H- O/CP. HNO were added to bring pH to 3.0 to 3.5. Materials were agitated at 5060C. and purged with N Ethylene oxide (29 gms from cylinder) were added. A total of 22.5 gms were absorbed.

The product was stripped to l 10C. pot temperature under line vacuum and then filtered.

The weight of the final product was 451 gms.

7r Nitrogen 4.8 Theory 5.07

The product generally corresponds to the formula:

0 cm '1 II F l [N KON-910410 (CHZCIIQOMJSTPWNHC 1L0 moms-on:

A total of 12.0 gms were required. The product was then stripped of water at 40 mm. pressure and the residue was filtered. The yield was 557 gms. Theoretical yield was 0.9 X 722 650 gms. so the yield was 85.8.

c. To a 2-liter 4 necked flask with joints clamped for slight pressure were charged 430 gms. 0.6 mol) of the above phosphonamide, 300 ml. H 0 and 300 gms. isopropanol. Then 40 gms. 85% phosphoric acid were added to bring pH to 3.0 to 3.5. Materials were agitated at 5060C. and purged with N Ethylene oxide (28 gms. from cylinder) were added. A total of 24.0 gms. were absorbed.

The product was stripped to 1 10C. pot temperature under line vacuum and then filtered.

The weight of the final product was 437 gms.

rate according to AATCC Standard Test Method The swatches were conditioned at 72F. and relativehumidity for at least 24 hours and the resistivity measured. Results were as follows:

Log Ohms/Square Dacron Cotton Control 13.46 14.24 Quaternary Phosphonamidc 8.96 8.87

a nitrogen 3.0 Theory =13 45 EXAMPLE The product was prepared as in Parts (a) and (b) of The product generally corresponds to the formula: Example I.

o1-I3 :l [CiI3(CH:)m-HO(CIIgQlIgOhas: NIICHQCHQCH:NCHQ EH1");-

Jg L H2OII'J"OH d. The quaternary formed above was applied from MeOH/CCl Nylon Faille and Dacron swatches at 1.25% application 1 rate according to AATCC Standart Test Method 76 1959.

Log Ohms/Square Nylon Faille Dacron Control (Untreated Fabric) 14.02 13.46 Quaternary phosphonamide 8.79 8.65

c. To a joints 2 liter 4 necked flask with hoints (520 mls/lOOO, mls) solvent mixture to 55 clamped for slight pressure were charged 430 gms (0.6

mole) of the'above carbamate, 300 ml H 0 and 300 gms isopropanol. Then 47.5 gms H SO were added to bring pH to 3.0 to 3.5. Materials were agitated at 50-60C. and purged with N Ethylene oxide (30.0 gms from cylinder) were added. A total of 26 gms were absorbed.

The product was stripped to 1 10C. put temperature under line vacuum and then filtered.

The weight of the final product was 440 gms.

7c Nitrogen 3.1 Theory 3.3

the product generally corresponds to the formula:

d. The quaternary formed above was applied from The product generally corresponds to the formula:

oin t 31 2)1 (CHQCHQOMTP Nl1Cll ClluCl1gNCll1 111W)!" Log Ohms/Square Nylon Faille Polypropylene Control 14.02 14.64 Quaternary Phosphonamide 8.85 9.10

EXAMPLE IV a. To a round bottom flask was charged a total of 306 parts by weight of an ethoxylate (4.0 mole E0.) of octyl alcohol. The ethoxylate was agitated at ambient temperature (30C) while 77 parts phosphorous oxychloride (0.5 ml) were dropped in over about 1.5 to 2.0 hours. After addition of phosphorous oxychloride was completed the batch was heated to 6070C and held one hour longer. Samples were then run and repeated at one hour intervals until the percent chlorine on hydrolyzed samples showed as low as theoretical.

b. To a breaker equipped with agitator. two dropping funnels. thermometer and a pH meter were charged 500 ml water and 91 gms dimethyl propylene diamine (0.9 mole). These materials were agitated at room temperature while 623 gms of the phosphonamide (0.9 mol) prepared in (a) and 30% NaOH were dropped in simultaneously over about 1 to 1.5 hours at such a rate as to maintain the pH between 10.0 to 10.5. A total of 108 gms 30% NaOH was required. After all reactants were added the batch was agitated 15 minutes at room temperature and then brought to pH 9.0 with CP HCl. A total of 13.0 gms were required. The product was then stripped of water at 40 mm pressure and the residue was filtered. The yield was 552 gms. Theoretical yield was 0.9 X 758 682 gms so the yield was 80.9.

c. To a 1 liter 4 necked flask with joints clamped for a slight pressure were charged 455 gms (0.6 mole) of the above phosphonamide 350 ml H 0 and 45 gms H PO to bring pH to 3.0 to 3.5. Materials were agitated at 50-60C and purged with N Ethylene oxide (33gms from cylinder) were added. A total of 26 gms were absorbed.

The product was stripped to 110C pot temperature under line vacuum and then filtered.

The weight of the final product was 460 gms.

'72 Nitrogen 2.9 Theory 3.1

d. The quaternary formed above was applied from MeOH CCl 52.0 mls 1.000 mls) solvent mixture to Dacron and Nylon Faille swatches at 2.5% application rate according to AATCC Standard Test Method 76-1959.

The swatches were conditioned at 72F and 50% relative humidity for at least 24 hours and the resistivity measured.

Results were as follows:

Log Ohms/Square Dacron Nylon Faille Control 13.46 14.02 Quaternary phosphonamidc 8.92 9.08

EXAMPLE V a. To a round bottom flask was charged a total of 660 parts by weight of an ethoxylate (10.0 moles E0) of nonyl phenol. The ethoxylate was agitated at ambient temperature (2030C) while 77 parts phosphorous o'xychloride (0.5 mol.) were dropped in over about 1.5 to 2.0 hours. After addition of phosphorous oxychloride was completed the batch was heated to 60-70C and held 1 hour. Dry nitrogen was then bubbled through the mixture and the temperature was maintained for one hour. Samples were then run and repeated at one hour intervals until the percent chlorine on hydrolized sample showed-as low as theoretical.

b. To a beaker equipped with agitator, two dropping funnels, thermometer and a pH meter were charged 700 ml water and 91 gms dimethyl propylene diamine (0.9 mole). These materials were agitated at room temperature while 1,260 gms of the chlorophosphonate (0.9 mol.) prepared in (a) and 30% NaOH were dropped in simultaneously over about 1 to 1.5 hours at such a rate as to maintain the pH between 10.5 to 11.0. A total of 150 gms 30% NaOH was required. After all reactants were added the batch was agitated 15 minutes at room temperature and then brought to pH 9.0 with CP HCl. A total of 12.0 gms were required. The product was then stripped of water at 40 mm pressure and the residue was filtered. The yield was 1.053 gms. Theoretical yield was 0.9 X 1466 1,320 gms so the yield was 79.8. 4

c. To a 2 liter 4 necked flask with joints clamped for slight pressure were charged 880 gms (0.6 mol) of the above phosphonamide, 400 ml H 0 and 400 gms [sopropanol. Then 40 gms Phosphoric Acid were added to bring pH to 3.0 to 3.5. Materials were agitated at 5060C and purged with N Eythlene oxide (28 gms. from cylinder) were added. A total of 24.0 gms were absorbed.

The product was stripped to 1 10C pot temperature under line vacuum and then filtered.

The weight of the final product was 886 gms.

propanol. Then 45 gms 85% Phosphoric Acid were Nitrogen 155 Theory added to bring pH to 3.0 to 3.5. Materials were agitated at 5060C andpurged with N Ethylene oxide (54 gms. from cylinder) were added. A total of 47.0 gms The product generally corresponds-to the formula: 5 were absorbed.

d. The quaternary formed above was applied from The product was stripped to 110C pot temperature MeOHCCL, (520 mls 1000 mls) solvent mixture to under line vacuum and then filtered. Polypropylene and Dacron swatches at 1.25% applica- The weight of the final product was 470 gms. tion rate according to AATCC Standard Test Method 76 l959' 7r Nitrogen 6.71 Theory 6.85

The swatches were conditioned at 72F and 50% re1- ative humidity for at least 24 hours and the resistivity The product generally corresponds to the formula:

. il l v y l [oimoumumo oinclnomfvzmrougoinouzu ou; 1121201 ClT2ClT:()l[ 2 measured. Results were as follows: I l d. The quaternary formed above was applied from Losohmslsquare 25 MeOHzCCL, 520m 1000 mls) solvent-mixture to cotton and Dacron swatches at 1.25% application rate Polypropylene Dacron according to AATCC Standard Test Method 76-1959. Control 14-64 13-46 The swatches were conditioned at 72F and 50% rel- Oumemary phmphonamde ative humidity for at least 24 hours and the resistivity EXAMPLE VI measured. Results were as follows:

a. To a round bottom flask was charged a total of 288 parts by weight of an ethoxylate (1.85 moles E0) of a C,,C, straight chain primary alcohol admixture calculated as a 209 MW. average and having the compo- Lo Ohms/Squa e sition 5% C 2570C 30%C 30%C and 1072C Y The ethoxylate was agitated at ambient temperature (20-30C) while 153 parts phosphorus oxychloride Cumm' 14424 1346 (1.0 mol.) were dropped in over about 1.5 to 2.0 hours. Oummnry phosphunum'dc After addition of phosphorous oxychloride was com- 40 pleted the batch was heated to 6070C and held 1 hour. Dry nitrogen was then bubbled through to mixture and the temperature was maintained for 1 hour. Samples were then run and repeated at l hour intervals until the percent chlorine on hydrolyzed sample showed as low as theoretical.

b. to a breaker equipped with agitator, two dropping Whatis claimed is: i 1, A compound of the formula:

funnels, thermometer and a pH meter were charged 0 a1 500 ml water and 182 gms dimethyl propylene diamine IFWCHZOHOM NH CH2CH2(J]I2 N:R2 (1.8 mole). These materials were agitated at room tem- I: :I R3 p perature while 364 gms of the chlorophosphonate (0.9 mol) prepared in (a) and 30% NaOH were dropped in simultaneously over about 1 to 1.5 hours at such a rate as to maintain the pH between 10.5 to 11.0. A total of 230 gms 30% NaOH was required. After all reactants wherein R represents an aIkyL'phenyl or alkylsubwere added the batch was agitated 15 minutes at room stituted phenyl radical having 7 to about 25 carbon temperature and thenbrought to pH 9.0 with CP HCl. atoms, X represents hydrogen, methyl or ethyl, R and A total of 22.0 gms were required. The product was R are members of the group consisting of alkyl and hythen stripped of water at 40 mm pressure and the residroxy alkyl radicals of from 1-3 carbon atoms, R is a due was filtered. The yield was 402 gms. Theoretical 6O hydroxy alkyl radical of from 14 carbon atoms, Y is yield was 0.9 X 536 482 gms so the yield was 83.3. an anion, m is an integer of from 1-10, n is an integer c. To a 1 liter 4 necked flask with joints clamped for of from 1-2, and p is an integer of from 1-2, and the slight pressure were charged 322 gms (0.6 mol) of the sum of'n p 3. above phosphonamide, 200 ml H 0 and 200 gms iso- 2. A compound of the formula:

3. A compund of the formula:

6. A compound of the formula:

7. A compound of the formula:

5. A compound of the formula:

(IJIIQCHQO ll UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Q PATENT NO. 2 3,856,895

DATED 3 December 24, 1974 E T()R(5) 3 Fred 5. Eisman, Jr.; L. M. Schenck; John P. G. Beiswanger It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

On the front page, after the listing of inventors, insert Assignee: GAF Corporation 0 New York, N.Y.--

Signed and Scaled this twenty-fourth Day Of February 1976 [SEAL] Arrest.

0 RUTH C. MrASON C. MARSHALL DANN Arresting Officer Commissioner oj'Parenrs and Trademarks

Claims

1. A COMPOUND OF THE FORMULA:

2. A compound of the formula:

3. A compund of the formula:

4. A compound of the formula:

5. A compound of the formula:

6. A compound of the formula:

7. A compound of the formula: