Eines Phosphate Esters: Chemistry and Properties By Anthony J. O'Lenick Jr. and Joffrey K. Parkinson, Si ssphato esters ara used in many textile applications because of various surfactant properties they pos sass. Of the desirable surface activo properties, alkali stability and we properties aro key. This work celates the structure of a phosphate ester to "hese tee prop chemistry Phosphate esters are part of a class of commercial products Abstract, Several near alcohol and linear alcohol ethoxylates were phosphated using P,0,, and the analytical results tor monoester,dlester and free Phosphoric acid content were determined as were wetting speed ‘and afkall tolerances. Generally, the Concentration of monoester and free Phosphoric acid Increased and the lester concentration decreased as oxide in the hydrophobe increased, the wetting time aise Increased, The lowest molecular weight hysrophobe ‘without ethylene oxide was the best ‘wetter in the series of nonethoxviated Species. As the molecular weight of the hydroshobe without ethylene ‘oxide increased, the wetting time of the phosphated material Increased A certain amount of ethylene oxide fon the hydrophobe was necessary to five the phasphated material alkall {olerance. As the molacular weight of the nusropheba heing phecohated Inerseass, the emourt of sylene evita peatiod te eavelop all tolerance inereacas. ‘The silicone phosphate esters appeared to fit the anticipated values for nkail tolerance, when compared to the fatty phosphates, when thelr ‘ethylene oxide content is considered, ' | ich inc., Norcross, Ga. ° ° ° 4 4 i ro#on ORCA todcn Row t fl 1 on on on Monoarar Closter From Prothane Aad Free Nonionte Fg, 1. Commercial products ara complex mixures of monoester, deste, fee phosphoric acid hhosphoric acid and fre nonionic a8 now in Fig. 1! i | Phosphating Reagent Polyphosphoric acid and phosphorous pentoxide (P,O,) are gonerally the two different phosphating agents used commercially (Fig. 2). The selection of the phosphating reagent has an effect ‘on the ratio of the components and on | | the functional properties of the fin ished product. Phosphorous pentoxide and a variety of linear alcohols and ‘othoxylatos of linear fatty alcohols, ‘wore chosen to determine the effect of allyl group and amount of ethylene ‘oxide on the resulting mono/di ratio and the amount of free phosphoric acid, as well as the effect on functional properties such as wetting and alkali tolerance. Chemica Analysis The pbosphation product was ana- lyzed for nono, i and free phossko- Fe acid concentrations using an acid ‘aiue titation method. Tis method dows not lly identify the product, ut| St icee give vaiable insights on the | prods’ quality. The titration Is run | "Table lt Results of Acid Value Anaiyata for Monoester, Dlestor ‘and Free Phosphorie Ac Materia Phosphated Fatty Alconel Phosphate Designation Hoey alohet ——_Hoxy9EC ahessnate Geylacons Cem DEO zheernata Secpaeenet ——-Baop DED. Been 2 male ‘inte Dec 2SED Gacys ate ‘omiale Deg 6EO acyl 3 mate ‘ehoniste Bess 80E0 Tedeoy aeanel Treacy OED Tadeo 8 mate scone Tadeo 8520 ayia alone! Mya 0 60 phoson Myra 3 mle ietionfate ——Mysyt 3 €O prospnata yet ate ‘shone Myre 7 £0 posphate yrs 8 meta ate Myst 9 EO phosonata yy 12 mole forte” Myésy 12 £0 posphate Sima showseSileane 9 phoshate ‘ince conve Slice @ chosphae using a standardized solution of base— most commonly sodium hydroxide There are three distinct endp the titration and by evaluating aach, information on product quality is ob tained, Two endpoints can be deter Moncester Oientor Phospole Acid en 9 £3 anotenate 412 ee 383, 73 av zhosonate a Nirem’9 20 onecenste % Anan 0 €9 ahesorat 33 Iran 12060 orga ue ‘Siicono 8 phessrate 369 5 7i 3 FLoH = Presshateg Aga —> RO= oH ans ROS SE, 5.2, Poeznaton reaction “Fabio, Results cf NaGH Tier Analysis Mumper_ NaOH otcarvona Thee oe 060 orarenta 5 9 DEO pronora 5 een EO sneer 0 Dec 25 eS presets 1d 10 2 ‘9 3 a & 8 £ rt 3 3 mined dizectly by titration to a pH ‘using a pH electrode. The third is de- termined indizectly afer the addition of calcium chloride. The acid gener- ated by the addition is titrated, The acid value (AV) calculations are shown, in Eqs. 1-3 AVE = mk of NaOH ta Pent A) ormatyN6.1) Wegiicraameen sans) Ext [V2 = (pot NAGH 9 Poe 8) Nermay 8.1) Wlegrarsanpen gray Fa. 2 ‘Ava «pet NACH Pon Cermasy 8.1) Wagh osansieh pans) E'S ‘The throe acid values reeult fom the three types of phosphate protons avall- dole on each species. Species with. three acid groups (Le., phosphoric, acid) have an AV1, AV2 and AV3 ‘Those with two acid groups have an AVL and AV2 (Le, mongester), while those with only one acid group (he. “J have only an AV. tis then possible to calculate the monoester, diester and free phosphoric acid con- tent. Table ! surmarizes phosphated ° eq? co | axe ant i Neweaeaton alcohols and athoxylates, and gives the designation used to refer to the prod- ucts. Table IT summarizes the results of the analysis for monoester, diester ee poephoric acid forthe phes- hates studied. Properties Akal Stabity| Alkall stability was evaluated by the [NaOH titer method. The method was ‘used to measure the concentration at waich tho phosphate ester remains clear in standard concentrations of NaOH. While exact numbers were not generated with this method, it served 8s a good screening method. ‘Three test solutions were prepared. NaOH was added at 4, 8 and 12% by weight. The solutions were verified by ‘uttation with standardized acid. Then, 10.0 g of each test solution was added to a test tube and 0.3 g of test phos- phate ester was also added. The tubes ‘wore shaken, After 30 minutes, the highest concentration tube which re- mained cl NaOH titer. Results are presented in Table HL. ‘Wetting Speed ‘The following solution was propared and tested for wetting: % Weight a0. 913 Test Phosphate Ester 0.5 A. cm denim disc wae selected for the evaluation. Prot ‘o the evaluation. amount of time It took for the disc to was recorded (Table V).[tshould bbe noted thatthe test phosphate ester was placed into solacion asthe potas- yr was recorded as the | Table V, Wetting Speed ‘carnone Waring i ony 0 £0 photcrato soos Ceynd EO prowprate hod ‘cy 0 €0 pros ow Decyt 25 26 prownat we Deep soeo prema = 10 GrenaaeOrrenras = 198 Thamcn DEO prompnate 13 of Mymen2oeOorencra 1 3 ynegt 7.0 EO presmrats ia Myrse 20 ED pnosorate Te prema edema 4 phosprate Bo ehoaonaa 2 Results and Discussion Product Composition ‘The concentration of monoester, di- estar and free phosphoric acid for the phosphate esters based on decyl alco- Lol and its ethoxylates are shown in Fig. 2 As the amount of ehvlene ox ide on the decyl alcobot hydrophobe ‘was increased from zero to seven moles ofethylene oxide, the concentration of monoester and free phosphoric acid increased in an almos linear fashion. The diester content dropped as the amount of ethylene oxide on the hydrophobe increased. Sinco all hydrophobes wore dried prior to phosphation, the increase was not at- Eibuted to the prosence of water The concentration of monoester. Fig 4s the anout of easion o ide on the myristyl alcohol hyd phobe was increased from zero to Seven moles of ethylene oxide, the con- centration of monoester and diester varied only slightly, but the trend was a sy wait STR Ta Sere Swi STI Tees Te Moses 20 Mons EO Fig. 4. Monoletastr ral ve. moles of ethylene cxide for Cre hyskophote, Fig. 2.9 Cro hyeropnobe, i Liem Mat ar ae3 | ia ome i | i ' } 0. Fo.5 Wee sped ofphscateaxors—untarct ato ans co eben od cont on wen e000 Fbenytepaoe wong ane a requited to render the phosphated ‘material alkali tolerant, As the molecu- lar weight of the hydrophobe being phosphated increased, the amount of ethylene oxide required for alkali tol- erancs also increased. Decy! alcohol phosphate containing eight moles of sthylene oxide had an alkali titer of 8 Effect of Ethoryltion con Wetting Speed ‘The ethoxylated materials all reached their fastest wetting times with be- tween two and three moles of ethylene matic drop in diester and increase in | oxide added within each set of monoester and free phosphoric acid | hydrophobes. Two different phos- resulted. Again, since all the hydro- | pated hydrophabes plotted against phobes ware dried prior to phos- | thoqumbor of moles of ethylene oxide Phation, the increase was not attrib- | added tothe hydrophobe, and the HLB Sted to the presence of water. It does | tke lcahol sthonylate are shown in for loss diester and more phoric acid as the amount while it took twelve moles of ethylene oxide.on myristyl alcohol to obtain the same level of alkali tolerance (Figs. 8 fppear however, that tbe more polar | Figs ¢ aad 7, rmpectively. The ues | 42) tlcohot ethoxylatss phosphate less_| “yas caleulated using % EO/S.Thofast- | fect of Ethorlation readily, producing more monoester | Yet wetting mes fall within the samo | on Alkali Tole of ethylene tid fro phosphoric aed than those See Phospoetion seactong-un using more | TNGe-sheyOeraecacclarnagne | TRO greater the degree of ethoxylation, Evdrophobic fay aleools or fatty | Gfthehydrphobe the ater he wat | the more alkali tolerance was ob- cohol ethoxylates has been sug: | sing me, What was not included in a eae See eee ae Pevaisigl | 2ng,tme, What was not included in | iyais tolerance with less than six en Ja this investigation. but appears interest” | roles of ethylene oxide. It also ap- (0 steric hinderance, Ing, is a hexyl 2-3 mole ethylene oxide sah oxide | peared that as one attempts to increase Effect o Ally! Group | ich would be predicted | thy wetting speed, alkali tolerance ‘on Wetting Speed decreased. Decyl aicohol phosphate As the molecular weight of the containing six moles of etiylene ox {de appeared to bea good compromise hydrophobe increased, the wetting | “The silicone phosphato estes ap- time Ukewise incensed. The lowest | peared te hte satcrpated values fr molecular weight hydrophobe (hexyl | fretting, when compared to the fatty phosphate) without ethylene oxide | Phosphates, when their ethyl ‘was the best wetter in the series of | content is consi ‘anticipated nonethoxzlated species. As the mo- | that lower amounts of ethylene oxide | TH Jculas woight of the bydrophobe | would give improved results | Balitolerance, when compared tothe the wetting time of the phosphated | Etfectot Alkyl Group | fay phosphates, when their ethylene product increased (Fig. 3). This was | on Alkall Tolerance oxide content is considered. true for hydrophebes having 6 t0 14 | — appeared that a certain amount of carbon atoms. suiylene oxide on the hydrophabe was for both properties. Alkall Tolerance of ‘oxida | Sifeone Phosphates Its anti icone phosphate esters ap- peared to ft the anticipated values for ® [$ave sasen See aaron aaa oe ne : Fig. 8, Socium nyeconice Barve. moles of ethylene oxide nthe Cre Fig, 7, Stet of HLB on weting space. staring rysopnede. November 1925. CD 6