Sulfates of monoethylenically unsaturated alcohols and the alkenoxylated adducts of said alcohols
United States Patent 1191 Steckler 1 Apr. 1,1975  
 [ SULFATES OF MONOETHYLENICALLY UNSATURATED ALCOHOLS AND THE ALKENOXYLATED ADDUCTS OF SAID ALCOHOLS [75] Inventor: Robert Steckler, Crofton, Md.  
 [73] Assignee: Alcolac Inc., Baltimore, Md.  
 [22] Filed: Jan. 5, 1973 [21] Appl. No.: 321,228  
 [52] US. Cl. 260/458, 260/79.3 M, 260/80.7l, 260/80.73, 260/85.7, 260/87.1, 260/87.5 R,  
 260/87.5 G, 260/457, 260/484 R, 260/611 A, 260/615 B, 260/964, 260/965 2,241,421 5/1941 Price ct al 260/458 2,677,700 5/1954 Jackson et al. 260/458 3,413,331 11/1968 Beiser et al. 260/458 3,778,479 12/1973 Morrisroe et al. 260/458 Primary Examiner-Bernard Helfin Assistant E.\&#39;aminerNorman Morgenstein Attorney, Agent, or FirmHenry B. Kellog; George L. Tone [57] ABSTRACT Monoethylenically unsaturated alcohols of from 3 to 12 carbon atoms or the alkenoxylated adducts of such alcohols are reacted with a sulfating agent, such as, for example, sulfamic acid in the presence of an organic amide, i.e., urea, etc., as a catalyst at a temperature of about 85 to about 125C. for a period of time sufficient to give a high degree of conversion as determined by the acid number of the reaction mixture. The resultingv monomers, which are useful as comonomers in emulsion polymerizations, as comonomers for the preparation of membranes and polyelectrolyte complexes, and as co-monomers which function as dye acceptors in the preparation of polymers from acrylonitrile, vinyl chloride, etc., for use as films and fibers, are characterized by the following formula:  
 wherein R is a radical selected from the group consisting of vinyl, allyl, propenyl, isopropenyl and styryl, R is either hydrogen, methyl or ethyl, m is a numeral of from 1 to 10, n is either zero or a numeral of from 1 to 100, and M is either ammonium or an alkali metal, e.g. sodium, potassium or lithium.  
 7 Claims, No Drawings I SULFATES OF MONOETHYLENICALLY UNSATURATED ALCOI -I QLS AND THE ALKENOXYLATED ADDUCTS OF SAID 1 ALCOHOLS 4 This invention relates to a new class&#39;of polymerizable ammonium and alkali metal salts of sulfated monoethylenically unsaturated alcohols of from 3 to 12 carbon atoms and of the alkenoxylated adducts of such alcohols.  
  The principal object of the present invention is to provide a new class of polymerizable monomers.  
  Other objects and advantages will become manifest from the following description.  
  It is known that polymerizable sulfo esters of alphamethylene carboxylic acids can be prepared by reacting an alpha-methylene carboxylic acid chloride such as acryloyl or methacryloyl chloride with an alkali metal salt of a hydroxy alkane sulfonic acid such as, for example, sodium isethionate while dispersed in an inert diluent at elevated temperature. The monomers thus prepared are sulfonates and not sulfates. The economic shortcoming in this preparation is the high cost of the alpha-methylene carboxylic acid chlorides as well as their toxic effect on human skin and mucous membrane.  
  l have found that polymerizable monomers of ammonium and alkali metal salts of monoethylenically unsaturated alcohols of from 3 to 12 carbon atoms and of the alkenoxylated adducts of such alcohols having the formula:  
 wherein R is a monoethylenically unsaturated radical selected from the group consisting of vinyl CH =CH, allyl CH =CHCH propenyl CH:,CH=CH-, isopropenyl CH2=C(CH and styryl C l-l CI-l= CH-; R is either hydrogen, methyl or ethyl; m is a numeral of from 1 to 10; n is either zero or a numeral of from I to l00 and M is either ammonium or an alkali metal, e.g., lithium, potassium or sodium, are prepared by reacting one mole of a monoethylenically unsaturated alcohol of from 3 to 12 carbon atoms or one mole of the alkenoxylated adduct of such alcohol with one mole in slight excess to about 2 moles of a sulfating agent such as, for example, sulfamic acid in the presence of an organic amide as a catalyst such as, for example, urea, acetamide, dicyandiamide, and the like, at a temperature ranging from about 85C. to about 125C, for a period of time sufficient to give a conversion of at least 80% preferably between 90 and 100% as determined by the acid number of the reaction mixture. The actual time may range from about 2 /2 to 4 hours.  
  The amount of catalyst that may be employed is variable and may range from about 0.01% to about 1% by weight based on the weight of the unsaturated alcohol or the alkenoxylated adduct of such alcohol.  
  Instead of sulfamic acid as the sulfating agent, chlorosulfonic acid, 80;, or oleum may be employed in the conventional manner.  
  As examples of the monoethylenically unsaturated alcohols employed in accordance with the present invention the following are illustrative: allyl alcohol, allyl carbinol, beta-allyl-cthyl alcohol, crotyl alcohol (2- buten-l-ol), methallyl alcohol, hexen-l-ol-6, hepten-lol-7, octen-l-ol-S, decen-l-ol-lO, undecylene alcohol (undecen-l-ol-l l dodecen-l-ol-lZ, tetradecen-l-oll4, cinnamyl alcohol, and the like. In addition to the latter alcohols, methyl-vinyl-carbinol, vinyl-ethylcarbinol and methyl allyl-carbinol may also be employed.  
  As noted above, the foregoing alcohols may be sulfated or the alcohols may be alkenoxylated with one to or more moles of an alkylene oxide such as ethylene oxide, 1,2-propylene oxide and 1,2-butylene oxide or mixture thereof and then sulfated. Alkylene oxides containing from 5 to 22 carbon atoms (i.e. when R in the above general formula may be an alkyl of from 5 to 22 carbon atoms) which are obtained by the epoxidation of straight or branched chained alpha-olefins by a peracid directly or by a chlorohydrin and caustic route may also be used. The epoxides may be derived from cracked wax and may contain both an even and odd number carbon atoms in the alkyl carbon chain. The odd-numbered alkylcarbon chain may also be derived from raw material originating either from the Ziegler synthesis (ethylene) or from fatty sources.  
  The preparation of the alkylene oxide adduct (alkenoxylation) of the monoethylenically unsaturated alcohol is conducted in the conventional manner.  
  The polymerizable monomers obtained in accordance with the present invention are useful, not only as co-polymerizable surfactants for self-stabilizing latexes, but also as comonomers in the copolymerization with other polymerizable monomers in the preparation of eoor ter-polymeric films and fibers, especially as reeeptors for basic dyes and to build in anti-static properties.  
  The monoethylenically unsaturated alcohols as well as the alkenoxylated adducts of such alcohols, instead of being converted into sulfates, can be phosphorylated with or 1 l5% super phosphoric acid under conditions known to the art to yield a mixture of monoand di-csters of phosphoric acid. The unsaturated alcohols and the alkenoxylated adducts of such alcohols can also be condensed with sodium-chloroacetate to form the corresponding glycollic acid esters. These esters as well as the monoand di-esters of phosphoric acid are also useful as co-monomers in emulsion polymerization, or as co-monomers in the preparation of membranes or polyelcctrolyte complexes and as dye accepting monomer in copolymerization with other monomers in the preparation of films and fibers.  
  The following examples will serve to further illustrate the invention, but are not to be construed in limitation thereof.  
 EXAMPLE I CH =CHCH O(CH C 4.2m a 4 lnto a one gallon capacity autoclave equipped with agitator thermometer, pressure gage, heating and cooling jacket (or coil), there were charged 285 gms. of allyl alcohol and 8.5 gms. of a 25% solution of sodium methylate in anhydrous methanol. After purging with nitrogen, the autoclave was heated under agitation to 4045C. while pulling sufficient vacuum to remove all methanol. The temperature was then raised to 75C. and nitrogen introduced to 10 psi pressure. During a two hour period, 1105 gms. of ethylene oxide were added gradually while raising the temperature to 135C. followed by holding one-half hour at that temperature. A small amount of unreacted ethylene oxide was removed by pulling vacuum, followed by cooling to room temperature during one hour. The reaction prod- 5 uct was then neutralized with 85% phosphoric acid to a pH of 5.7.  
  The resulting allyl alcohol ethoxylate showed a hydroxyl value of 206.1; molecular weight of 272 and an iodine value of 84.8. It was free from unreacted allyl alcohol. The average composition was 4.86 moles of ethylene oxide per mole of allyl alcohol.  
  Into a 1000 ml. 3-necked flask equipped with thermometer agitator and electric heating mantle, there were added 200 gms. of the resulting allyl alcohol polyethoxylate, 102 gms.( 1.05 moles) of sulfamic acid and 3 gms. of urea and the mixture heated in a nitrogen atmosphere to l l0l20C. until the acid number remained constant and a sample formed a clear solution in water. To the reaction product were added 278 gms.  
 of water and 17 gms. of aqueous ammonium hydroxide solution. The solution was clear, reddish in color and had a pH of 7. 1t contained 32% active allyl alcohol polyethoxysulfate ammonium salt. The iodine value was found to be 84.4 indicating a retention of the 25 original monoethylenic unsaturation.  
 EXAMPLE 11 CH CH=CHCH -O(CH CH O) SO,,NH  
  72 gms. of crotyl alcohol were reacted with 2.25 gms. of sodium methylate in anhydrous methanol and 2200 gms. of ethylene oxide as in Example 1 The neutralized polyethoxylate has a pH of 6.5; a hydroxyl value of 25.1  
 and a molecular weight of 2235. The average composi- 35 gms. of sulfamic acid and 0.27 gms. of urea. The purple reaction product was dissolved in water and the nonvolatilcs adjusted to 30?! active and the pH to 7.6. A clear reddish solution was obtained.  
 weight of 1295. The average composition was 25 moles of ethylene oxide per mole of hexen-l-ol-6.  
  254 gms. of the resulting product were reacted with 20 gms. of sulfamic acid and 0.5 gms. of urea as in Example l. The somewhat dark purple product was dissolved in water and the pH and non-volatile adjusted to 30% active and a pH of 7.5. A clear reddish solution was obtained.  
 EXAMPLE 1V 134 gms. of cinnamyl alcohol, 5 gms. of 25% solution of sodium methylate in anhydrous methanol and l 100 gms. of ethylene oxide were reacted as in Example 1. The neutralized polyethoxylate showed a pH of 6.3; hydroxyl value of 45.9and a molecular weight of 1221. The average composition was 24.7 moles of ethylene oxide per mole of cinnamyl alcohol.  
  200 gms. of the resulting polyethoxylated cinnamyl alcohol, 16.7 gms. of sulfamic acid and 0.5 gms. of urea were heated in a flask under a nitrogen atmosphere to l l0l20C. until the acid number remained constant and a sample formed a clear solution in water. The reaction product was diluted with water to yield a 30% active solution and the pH adjusted to 7.3 with aqueous ammonium hydroxide solution. The latter solution was clear and of reddish color.  
 EXAMPLE V CH =CH(CH --O-SO N H One mole (170 gms) of undecenyl alcohol, 102 gms.( 1.05 moles) of sulfamic acid and 3 gms. of urea were heated in a flask under a nitrogen atmosphere to 1 l0l20C. until the acid number remained constant and a sample formed a clear solution in water. To the reaction product were added 278 gms. of water and 17 gms. of 30% aqueous ammonium hydroxide solution. The solution was clear, reddish in color with a pH of 7.0 and contained 33.3% active undecenyl alcohol sulfate ammonium salt. The iodine value of the active material was found to be 62.3 thus indicating retention of the original unsaturation.  
  Into an autoclave as in Example 1 there were loaded 595 gms. (3.5 moles) of undecenyl alcohol and 8 gms. of a solution of 25% sodium methylate in anhydrous methanol. The reactor was evacuated and the methanol removed by heating to 100C. and holding it at that temperature for 20 minutes with a vacuum of about 5 mm. The reactor was then charged with nitrogen until a pressure of 10 psi was obtained and then 1840 gms. (42 moles) of ehtylene oxide were added during 1% hours while gradually increasing the temperature to [C. After completion of this cycle, the batch was held for another 30 minutes at 170C. The unreacted ethylene oxide was then removed by pulling vacuum while cooling to room temperature during one hour.  
 The reaction product as neutralized with 2.8 gms. of I lactic acid and showed a hydroxyl value of 78.5,  
 indicating a 12.28 mole ethoxylate. The molecular weight of the product was 714.7.  
  268.3 gms. of the neutralized reaction product were added into a three-neck flask equipped with an agitator and 52.5 gms. of chlorosulfonic acid added drop-wise during one hour at 3035C., while cooling the flask in an ice bath as needed and the liberated hydrogen chloride gas removed by purging with air. After completion of the addition, air purging was continued for one-half hour. The resulting sulfate ester was neutralized by pouring 272 gms. of it into a solution of 575 gms. of water and 36.3 gms. of 50% sodium hydroxide. The final product was adjusted by the addition of 3 volatile content of the solution was 32.2% consisting primarily of 31.1% of the sodium sulfate of the polyethoxylated alcohol, 0.54% of unreacted nonionic. i.e. polyethoxylated undecenyl alcohol, 0.28% of sodium sulfate and 0.28% of sodium chloride. The solution was straw colored.  
 EXAMPLE Vll 250 parts by weight of water, 95 parts by weight of vinyl chloride and parts by weight of the final product of Example V (containing five parts by weight of active non-volatiles) were charged into an autoclave as employed in Example I, and the charge heated to 5055C. for hours under agitation. After cooling to room temperature, the autoclave was vented to release any unreacted vinyl chloride monomer. The vinyl chloride-ammonium sulfate salt of undecenyl alcohol copolymer latex obtained showed excellent mechanical stability. The composition of the copolymer was 95.6% vinyl chloride and 4.4% of the ammonium undecenyl sulfate. The yield was 92%.  
 EXAMPLE Vlll Example Vll was repeated with the exception that the 15 parts by weight of the final product of Example V were replaced with 15.5 parts by weight of the final product of Example Vl containing five parts by weight of active nonvolatiles. The stable latex showed a con.- version of 98% to a copolymer with a composition of 95.2% vinyl chloride and 4.8% of the sodium sulfate of the polyethoxylated undecenyl alcohol, i.e., final product of Example Vl.  
 EXAMPLE lX Example Vll was again repeated with the exception that the 15 parts by weight of the Final product of Example V were replaced with 16.7 parts by weight of the ammonium sulfate salt of the polyethoxylatedcrotyl alcohol of Example ll containing five parts by weight of active non-volatiles. The stable latex showed a conversion of 84% to a copolymer with a composition of 94.4% vinyl chloride and 5.6% of the ammonium sulfate salt of the polyethoxylated crotyl alcohol.  
 EXAMPLE X Into a three neck flask equipped with an agitator there were charged 425.7 gms. of water, 18.6 gms. of the sodium sulfate of the polyethoxylated undecenyl alcohol of Example V1, 210 gms. of 2-cthyl hcxyl acrylate, 87 gms. of ethyl acrylate and 3 gms. of a 60% aqueous solution of N-methylol acrylamide. Agitation was initiated for a few minutes while sparging with nitrogen. The resulting uniform emulsion was heated to 60C and 3.6 gms. of 10% aqueous sodium persulfate added. The batch was kept at 60-65C. for 3 /2 hours.  
 After cooling to room temperature, the emulsion contained 40.2% of tetrapolymer solids. The tetrapolymer had a pH of 7.1, a viscosity of 45 cps (Brookfleld 60 rpm, Spindle No.1) and a surface tension of 57.8 dynes/cm.  
 EXAMPLE Xl Into a three neck flask equipped with an agitator there were added 191 gms. of water and 41.7 gms. of the ammonium sulfate salt of the polyethoxylated allyl .alcohol of Example 1. The solution was purged with nitrogen for 20 minutes. Sixty five gms. of vinyl acetate were added and emulsified while purging with nitrogen and agitating for five minutes. The batch was heated to C. and 1 gm. of sodium bisulfite added, followed by 5 ml. of 2% aqueous sodium bisulfite solution. After a few minutes, the temperature began to rise exothermically to C. An additional 185 gms. of vinyl acetate and 45 gms. ofa 2% aqueous solution of sodium bisulfite were added gradually during minutes, during which time the temperature was allowed to increase to 6265C. After the addition was completed, the batch was heated to C. and held for one hour. The batch was cooled to room temperature. The resulting latex contained 52% copolymer. The copolymer showed excellent mechanical stability in the Waring blender and was uneffected during 20 minutes of high speed blending. The latex deposited clear films on glass.  
 EXAMPLE Xll 375 parts by weight of water, parts by weight of vinyl chloride, 1.5 parts by weight of potassium persulfate and 37.5 parts by weight of the ammonium sulfate salt of the polyethoxylated cinnamyl alcohol of Example lV (containing 6 parts by weight of the active nonvolatiles) were charged into an autoclave as in Example I and heated to 55C. for approximately 24 hours with constant agitation. After cooling to room temperature, the autoclave was vented to release any unreacted vinyl chloride monomer. The vinyl chloride-ammonium sulfate of the polyethoxylated cinnamyl alcohol copolymer latex showed excellent mechanical stability. The composition of the copolymer was 94% vinyl chloride and 6% of the ammonium sulfate salt of the polyethoxylated cinnamyl alcohol.  
  It is to be noted that the ammonium sulfate monomers of Examples 1 to V inclusive, after cooling to room temperature. may be converted to the corresponding alkali metal salts by the addition of the required amount of aqueous alkali metal hydroxide and then heating to about 60-75C. to remove the ammonia and then cooling to room temperature.  
 EXAMPLE Xlll Into a one gallon autoclave equipped with agitator, thermometer, pressure gage. heating and cooling jacket, there were charged 100 gms. of allyl alcohol and 1 gm. of sodium methylate powder. After purging with nitrogen. the autoclave was heated under agitation to C., and l 100 gms. of butylcne oxide added gradually at that temperature during 6 hours. Excess, unreacted butylene oxide was removed in vacuo and the batch cooled to room temperature. The low viscosity, light straw-colored liquid analyzed to be the adduct of 6 moles butylene oxide onto 1 mole of allyl alcohol. The molecular weight was found to be 488.  
  200 gms. of the above adduct and 0.4 gm. of sodium methylate powder were charged into the autoclave, purged with nitrogen and heated to 180C. 225 gms. of ethylene oxide were added during 9 hours at 180C. After stripping off the unreacted ethylene oxide in vacuo and cooling to room temperature, a low viscosity, clear, straw-colored oil was obtained which analyzed to be the adduct of 12 moles of ethylene oxide onto the adduct of 6 moles of butylene oxide and 1 mole of allyl alcohol. 250 gms. of this adduct were mixed with 250 gms. of methylene chloride at 25C. in a three-neck 1,000 ml. flask equipped with agitation. 35.5 gms. of chlorosulfonic acid were added during 15 minutes while cooling the flask in an ice bath. Hydro- I claim: I. A polymerizable monomer having the following general formula:  
 wherein R is a radical selected from the group consisting of vinyl. allyl. propenyl and isopropenyl, R is either hydrogen, methyl or ethyl. m is an integer of from I to l(), n is a numeral ranging from zero to I00, and M is a salt forming cation selected from the class consisting of ammonium and alkali metal.  
  2. A polymerizable monomer, as defined in claim I. having the following general formula:  
 wherein R is a member of the group consisting of hydrogen, methyl and ethyl. m is an integer of from I to 10, n is a numeral ranging from zero to l()(), and M is a salt forming cation selected from the class consisting of ammonium and alkali metal.  
  3. A polymerizable monomer. as defined in claim 1. having the following general formula:  
 wherein R is a member of the group consisting of hydrogen, methyl and ethyl, n is a numeral ranging from zero to 100, and M is a salt forming cation selected from the class consisting of ammonium and alkali metal.  
  4. A polymerizable monomer having the following formula:  
 CH =CH(CH ),,O(CH CH O-) SO Na.  
  5. A polymerizable monomer having the following formula:  
 CH =CH(CH OSO NH 6. A polymcrizable monomer having the following formula:  
 CH,-,-CH=CHCH O(CH -CH O-) SO NH 7. A polymerizable monomer having the following formula:  
  UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,875, 202  
 DATED April 1, 1975 |NVENTOR(5) 1 Robert Steckler It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 3, line +6, that portion of the formula reading (CH -CH -O 25 SO NH shoulo read (CH -CH -W- SO NH Signed and Scaled this fourth Day of November1975 [sen] I Attest:  
 RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oflarenls and Trademark;