. .4. I . . 4 . I . y . ‘ C .1... ...._ .nu-uk.... 4.3.... . . ‘ , . . fi . . . . .. ..... ....>. .... . ‘ f .42... 7. . .... ‘.........:.-. EMULSION POLIKERIZATION OF STIRENE BY POTASSIUH PERSULFATE CATALYST WITH REFERENCE TO CATALYST CONCENTRATION, NITROGEN, AND AIR Amosmmm THESIS FOR THE DEGREE 0F “.5. EICHIGAN STATE COLLEGE PAO-TSE YANG 19h? \"\ Acknowledgement The writer wishes to express his deep indebtednou to Dr. R. In. GUI-18 Md Dr. R. 00 am for their “'10. and suggestions. ”I” ~i 33.1. ‘ 8 Contents 228.! IntrwmeOOOOOOOOOQOOOO0.000000000000COOOOOO00000.... 1 Hiataric.1ooooo0.900000...00000000000000.9000...oto.0.5.. 2.6 Experimental: BO‘ECDt.oooooaoooooo-c00.000.00.00...tootoooooooooooooo 1.8 Eqniplent...o.......................................... 8 Procedure..............................o............... 8-15 Graphs............................o....................16-20 Ditcualicn......o.................d.....o...........o....21~25 can¢1uflianlgcoocoococooaooooooooocooooooo0000000000000... 27 Bihliogrlphy...........................t.................28-30 Introduction The purpose of this work was to continue investigation on emulsion polymerisation of styrene. Since there are many factors which influence the reaction, this particular work was limited to the study of the effects of catalyst concentration, nitrogen and air ataospheres. Other factors such as ratio of monomer to aqueous, mulsii‘ying agent, reaction tanperature, and the rate of stirring sore kept cmstant. Ithe catalyst chosen as potassium pet-sulfate shich has been used extensively for uulsion polyserisations. The emulsfier chosen was Duponol G, a soil- fonsted lauryl alcohol, shich is a good emulsifier for a styrcnednter system. The method «played in this see-k was to sample a polynerising mix- ture at various time intervals, precipitate the polymer and neasure its molecular night. The method gives comparable results and can be used to study the com-es of the reaction. Historical Styrene (originally named styrolen or styrol) eas first obtained as a distillation product. from gun atom. It as observed by Semen as far back as 186'! that styrene from natural somes solidified due to the effects or heat and lightl. In the same year, Berthalot syn- thesised styrue tr. acetylene and Ira ethyl bensenez’z. He men- tinned that synthetic styrene toned poly-era by reaction with sul- furic acid. He also discussed its polymerisation as sell as the polaaerisation of acetyleaez’h. With further advances in the study of poly-«issues of unsaturated hydrocarbons, styrene home we of the m upon-tent mono-um in the field a: polymerisations’9. The polyurisation of styrene in mgeneous liquid phase has been studied in bulk or in solutims of alcohol, toluene, carbon tetra- chloridelo and bemenen. In general, the polymerisation of styrene is catalyzed by heat, iigbtlz, «abon'n‘, organic pea-aim“, alkali metals16 , sine chlu'ide17. stumio chloride18 , titanium chla-ide19 , bimuth chloridezo, diumim compounds”) hydrogen fluoridezz, per- ba‘ate tee-pounds”, phosphates“, etc. Oxidation and reduction cata- lysts sore also aentimed in 'reduction activatim polaasrisatim' 25. Polamisation is considered to take place by three steps; namely, activation, propagation and terminatien2648. m aechanisms have been prep“ for the activation process: (a) tree redial (b) ionicza’zg. Propagatim consists of grssth of chain, branching of chain and cross- linking of chain. hark, Hohenstein and collaborators? reported that polyuerisation can he needs to take place in a tee phase system 1.13., in either a suspension 3' an emulsion. Emulsion polymerisation sac reported in 1915 for the synthesis or now-3°. liar): and 3.1131 describe an emulsion polymerisation system misting or sooner, emulsifying agent, stabiliser, eta-face regulator, catalysts, chain regulator, and buffer. The emulsion poly- serisation of styrene has been covered by many patents32 4'1. Many patents have been granted also on the copolyuerisation of styrme with other smsu‘u. Catalysts in emulsion polymerisation are usually of the ester soluble type such as twdrogen peroxide or salts of peracids. "01' the latter type, potassium persulfate is at the present tine the ’ soot sidely usedm’. The emulsifying agents are usually soaps or sul- i‘onated aliphatic alcohols. The polymer torsed remains in later fora which can be coagulated by heating, by additim of salt solutim or by organic solvents such as alcohol, other, etc. Fryling described a procedure {or studying eaulsion polymerisation in 19“.“. Hohenstein, Hark and collabuatorsw reported that emulsion polymer- isationotstyrenetakesplaceintheaquaousphase. Ithasbesnshosn byupsrilants thatshesstyrenedifi’usestrapureaonmerthrougha’ vapCphaseintoanaqueousphase,polyaeristmdintheaoueousphass. mania” shared that the solubilisation of styrene in soap dispersions takes place through swelling of the soap sicelles in the styrene portion. Gee"8 observed the polymerisation of. an unsaturated fatty acid at the interface or eater-air to take place in a nonmolecular film. Hohonstein then suggested the orientation and polymerisation of monomer within micelles. This orientation is assumed to be respmsible for the drop of the activation energy from 25,000 cal (in solutiui) to about 17,000 cal per sol (in emulsion)“. -3- byling and Harrington“9 supported the aicelle theory. This suppa't was based on the observation that pH value changed in emulsion polyaerisatim. They shoved that the addition of sonoser to aqueous soap solution is escapenied by too changes in pH value, an initial de- crease shich is attributed to solubilisation with the formation of sicellss in the aquews phase and a later increase which is the result of solution of fatty acids in the monomer phase. They also noticed that the decrease in pH (lining the course of polymerisation may be due to the transfer of fstty acid to the aqueous phase. The increase in pH toward the end of the reaction may be due to complete utilisation of the more. Oxidation, hydrolysis, and the adsorption of soap n the latex particles caplicate the pH effect in mulsion polymerisation. W50 and pH value as the measure or oxidation potential in his study of emulsion polyaerisatial. F He reported that there is a animus potential which is due to the inter- action between soap and persulfate, and since the yield-sauna occur in approximately the same region, he concluded that the reaction product of soap and persulfate is capable of initiating polyserisation. In esul- sion polymerisation soap acts to bring the manner into the aqueous phase where close contact is established with the activating radical. Soap also stetilises the late: to prevent polymer particles fra coalesc- ing. Monomers capable of undergoing bulk or mass polymerisation will do so to some content during emulsion polymerisation, and thus under oer- tain conditions, both bulk and wulsion processes say go at comparable rates in the sens reaction. 4.. Siggia investigated the diffusion process of monomer into the aqueous phase by determining the decrease of the monomer particle sise and the increase of the lumber of total particles (monomer and polymer) during the emulsion polymerisation.S 1. Recently, l-Iarkins52 pointed out that monomer molecules diffused through a thick diffused layer into (1) the aqueous phase, in which sane polymer particle nuclei were initiated, (2) soap miscelles, in which new polymer particle nuclei are initiated, and (3) into polymerisation particles after they are first formed by (2) or (1). Polymer formation on polymer particles is the locus for the naJm' pation of the poly-aeri- aation process. The production of polymer depends upon the number of particles initiated and is almost propa'tional to the initial amount of soap per unit mount of monomer. Very little polymer is formed in the monomer emulsion droplets due to the small number of free radicals present. ‘ The general principle of activation, propagation and termination is also applicable to the mechanism of snulsim polymerisation. Hohen- stein, Siggia and Mark“6 reported that in the course of mulsion polymer- isation, there is alsays an inhibition period, then the steady reaction period, and finally the termination period. Inhibition period is the tine necessary for at least the naJor portion of the monomer to free itself free: the presence of inhibitor, so that the fmation of long chains true the purified monomer may begin. mes1 pointed out um. the impurities in the mother and oxygen in the water are the causes of inhibition. The slower rate of diffusion of monomer soluble inhibitors frm the droplets into the highly dispersed eaulsion is responsible for .5... slower appearance of a critical inhibition concentration. A system of a higher soap-monomer ratio having a larger specific interracial area is capable of a faster nuclei formation and consumes the voter soluble inhibitor more rapidly than a system of lower soap monomer ratio. By using purified styrene, by excluding oxygen ”on the sys— tem, and by increasing the temperature, the inhibition period can be reduced. From a kinetic study of mulsion polymerisation, Kolthoi‘tls3 and hie-5" reputed that the steady rate, or polyuriaation in amino is propa'tionol to the some root of the concentration of potassium persnlfate. Rate of polymerisation is not effected by a chain regu- lator ouch as nsrcaptan and is not dependent on nonmer concentration. The relation of rate of conversion to the average aolecular night was studied by Biggie, Hohenstein and lax-é. It no found that the molecular weight of polymer toned during the period inediately after the start of the conversion is canparatively low. This is due to edeactivatim by inhibitor. Following the initial phase, the solo- cular weight increases oith a em rate to reach a maximum. Finally, the molecular weight decreases due to a decrease or mono-er cmcentra- tion and the increase of chain breaking decomposition products. Oxygen deactivatim has been studied by Barnesss, oho stated that pea-aide. are foraed. These peroxides are incapable of activation and are thus incapableottakingpartinpolyaeriaation. Thoynoy, however, aotas deactivating or terminating agents. shim56 shared that the average molecular night of a polymer is related to the ratio of war to regulator. -6- mental m Styrene - The styrene used see obtained from Eastman Kodak (inhibited with tertiary butylcatechol). It was freshly distilled fr:- a one-liter Claisen flask modified by a 16" Vigreau column. To prevent polymerisation during distillation, 30 g. of hydroquinone was added fa each 500 cc.‘ of styrene. A fractionboiling lhjz-lhhzc. at 716 m. and having a refractive index of 1.5h20 at 20°C. on col- looted. The fraction sas sashed alternately with 5; sodium hydruide solution and water until the alkaline sash showed no coloration and thenmhedfresofalkalibysater. Themhedstyrenesasdried Iith anhydrous sodium sulfate and stored in a refrigerator. The styrene sas stored no longer than a seek before use. Dupenol G - Duponol G , a sulfonated derivative of technical lauryl alcohol node by DuPont Company, one used as an onulsified, because it goveagoed stable enulsimbe’oseen‘bethaonaerandsatorsndpolyler and rotor. the Duponol G emulsifier as used as a 1% aqueous solution. (Sue other cmercial emulsifiers sore tested with the fixed styrene- tater ratiotof 1:8 and varied amounts of emulsifier, fro- 0.11 to 1% but they sore found unsatisfactory. The emulsifiers tested were Triton 720. Triton 770, men 20, man 60, Tseen 80, Racconol LAL, tin-sol u, Ansel 01', sodium cleats, ethanohnine and phenyl acetic acid, tri- ethanolanine and toluic acid, styrene naleic acid ccpolyner, Duponol 80 and polyvinyl alcohol. Potassiu- persulfate — Potassixm persulfate Merck C. P. grade no selected as the catalyst. Toluene - The toluene used in molecular weight determination by viscosity method was Eastssn C. P. grade. It was distilled collecting a fraction boiling 108°-108.5°c. at‘7h5 m. Ethyl alcohol - The alcohol used in precipitation of the polymer was ordinary commercial 95% material. All polymerisations were carried out in a four-necked, one-liter flask with ground glass Joints. The flask was fitted with condenser, wator sealed stirrer, thermometer and a 2 mm. glass tube. The tube was connected to a 200 cc. Erlenmeyer flask which could be partially evacua- ted; thus siphoning a sample into the flask at any desired time. The reaction flask was immersed in a constant tenperature bath. The tuperaturo of the bath was set at 60° . :(0.5°). A cylinder -of nitrogen (oil pumped) connected to a train consisting of a 500 cc. bottle of saturated alkaline pyrogallic acid solution and a 500 cc. eapty bottle was used in all cases where pdyzerisation oas carried out under nitrogen ataosphere. A Bechannpflneterwasused formsuringfliepfivalueofthe emulsion (hiring the course of polynerisatim. the precipitated polymer as separated by means of a centrifuge. A Cannon-Fenske-Oswdd viscosity pipette with K of 100 was used for the determinatim of average molecular weights of polystyrene by the viscosity method. Procedure Twelve to 11; labeled sample flasks (200 cc. corked Erlenmeyers) each containing 75 cc. of 95% alcohol were weighed to 0.1 g. -8- 80 grams of styrene and 320 g. of Duponol 0. solution were poured into the reaction flask which was iamersed in the constant temperature bath at 60°C. The potassiua persulfate weighed to .01 g. in amounts fr. 0.8 to 0.1 g. was dissolved with stirring in 320 g. of Duponol G solution. When the potassium persulfate was cmpletely dissolved, the solution was added to the styrene-Dupmol 0 mixture alreaw in the re- action flask. The tins of sdditim was recorded. The mixture was stirred at a constant rate during the reaction. it known tine intervals, the reaction mixture was sampled into the weighed and labeled flasks. At the same time, other small portions of the reactim mixture were taken for determination of the pH values. The sample flasks and contents were reweighed. The amount of each sample was determined by weight difference. After weighing, the ample was diluted with three times its volume of alcohol. This often coagu- lated the polymer. In case the coagulation did not occur, from 20 to 50 drops of concentrated hydrochlm'ie acid were added gradually to the snulsim and shaken until the coagulation started. The precipitated} aixttn-e was poured into a conical centrifuge tube and centrifuged. ‘ifter centrifuging, the clear supernatent liquid was restored by decan- tation. The precipitated polymer was washed several times with alcohol to remove emulsifier and was then dried in a drying row. The dried polyner of styrene was weighed. The percentage of polymerisation was calculated as follows: i of polymerisatim 3 100 I The wei ht of 01 or {- Thewe ht of the mixture The weIgHt' a empllne The w of styrene used The beginning of polymerisationlwas determined by adding to alcohol very small samples of the reaction mixture until a visible quantity of polymer precipitated. Accurate sapling was initiated at this point. The tine interval fu- sampling was adJusted such that fro- 0 to 100% polynerisatim about ten samples (25 to 50g. of each sample) could be obtained. the average aolecular weight or the polymer was determined by Standinger's viscosity nethod. Into a 200 cc. volumetric flask was placed 0.2082 g. of polystyrene. The polystyrene was dissolved by 10 cc. of toluene; the solution being left in a hot room overnight. By diluting with nor. toluene, the poly- styrene solution ”was then made up accurately to 200 cc. at 20°C. Ten milliliters of the solution were transferred into the viscosity pipette and the viscosity of the solution was measured by noting the tins of effluat20° . Tine of ernumreoordodtoonetonthoramondby leans ofatinsr. fheviscosityofthe tolumewasdeteniinedinthe sane any. The average aolecular weight was then calculated fra Standinger's equation: .112 I: ‘30 Where I : average nolecular weight. 0 2 molar concentration of polystyrene in toluene solution I 3 1.8 x 10"}; zine of efflux of solution at 20° . _ 1 N sp : Time of efflux of solvent “16657 Following the procedure as desdribed above, several systm were studied and the results tabulsted. -10- Experiments General Data Reaction Temperature 60°C . Styrene 80g: 11 Dupmol 0 solution 6150 gs Specific Data Part A - Air ltaosphere kperinents #1 and #2 _ Potassium persultate used .. 0.8 g. (0.00116 mole) No. l M 3:; pH % of P Av. 16. W. at; pH 2 of P 0.5 7.6 0.5 7.1 0.7 1.0 7.0 1.t 1.0 6.6 1.1 1.5 6.6 3.1. ' 1.5 5.8 2.9 2.0 6.1 9.0 105,000 ' 2.0 6.0 7.2 2.5 5.3 19.8 96,700 2.5 h.2 5.9 3.0 3.6 u9.0 110,000 3.0 3.0 9.5 3.5 3.6 69.0 110,000 3.5 2.9 1h.h 11.0 3.1 72.7 96,000 to 2.9 29.9 ' us 2.8 77.1; 81,600 h.5 2.6 5h.1 5.0 2.8 79.2 93.900 5.0 2.1; 82.8 5.5 2.6 90.0 73.300 5.5 2.2 89.2 6.5 2.5 91.3 72,800 P represents polymerisation Av. 11. W. is the average molecular weight. Av. H. F. 57,200 109,000 101,700 96,700 Part A. - Air Atmosphere (‘cont'~d.) moriments f3. #11 and #5 Potassium persuli‘ate used. .- 0.6 g. (0.00311 mole) Tine (hr) 1.25 2.00 2.50 3.00 3.50 3.75 h.oo h.25 8.60 5.00 5.50 6.h0 2.00 2.5 2.75 3.00 3.30 1.66 h.50 5.00 5.30 6.00 pH 7.3 6.8 6.h 5.6 h.h 3.9 3.6 2.6 2.11 2.8 2.6 7.0 7.2 6.9 6.7 6.5 5.8 ke3 3.6 3.0 2.8 12.2 i of P 3.6 5.6 6.1 10.8 15.5 28.1 39.2 55.8 68.h 78.5 83.8 86.2 no. 5 1.2 13.8 59.7 68.5 65.5 68.8 70.2 71.3 72.0 72.0 A's He we h2,200 105.500 110,600 122,000 98.000 105,500 100,000 107,000 128,000 Bh,h00 8h,h00 Time (hr) 0.85 0.91 2.17 2.66 3.33 3.66 1.33 h.66 5.17 5.66 6.66 pH 7.7 7.5 6.5 5.h 3.8 3.5 3.2 3.0 3.0 2.9 2.5 No. h 5 0: P 0.9 2.7 5.0 6.8 11.0 18.1 32.0 83.2 88.5 85.3 A's 1!. We 25,800 61,200 4 71,700 81,600 57.300 Part 1. - 1.1:- Atmosphere (cont id.) Experiments £3, #11 and #5 Potassium persulfate used... 0.6 g. (0.003).; mole) Tine (hr) 1.25 2.00 2.50 3.00 3.50 3.75 8.00 h.25 8.60 5.00 5.50 6.h0 2.00 2.5 2.75 3.00 3.30 1.66 h.50 5.00 5.30 6.00 pH 7.3 6.8 6.h 5.6 huh 3.9 3.6 2.6 2.h 2.h 2.6 7.0 7.2 6.9 6.7 6.5 5.8 h-3 3.6 3.0 2.8 No. 3 5 of P 3.6 5.6 6.1 10.8 15.5 2h.1 39.2 55.8 68.h 7h.5 83.8 86.2 Ho. 5 1.2 13.8 59.7 61.5 65.5 68.6 70.2 71.3 72.0 72.0 Av. n. W. 82.200 62,600 105,500 110,600 122,000 98,000 105,500 100,000 107,000 128,000 Bh.h00 8h,hoo Time (hr) 0.85 0.91 2.17 2.66 3.33 3.66 8.33 h.66 5.17 5.66 6.66 .12- pH 7.7 7.5 6.5 5.h 3.8 3.5 3.2 3.0 3.0 2.9 2.5 No. h 3 of P 0.9 2.7 5.0 6.8 11.0 18.1 32.0 83.2 88.5 85.3 A's Me We 25,800 61,200 " 71,700 81,600 57.300 Part.l -»Air Atmosphere Experiments #6, #7 and.#8 Potassim persulfate used = 0.8 2- (0.0023 mole) tile (hr) 2.0 3.0 3.5 8.0 8.5 5.5 6.0 ~ 6.5 7.5 8.0 8.5 9.0 10.0 1.05 2.16 3.20 8.05 6.05 6.55 7.05 7.55 8.80 28.0 pH 7.1 6.7 6.7 6.8 5.8 5.0 8.6 3.7 5.6 3.8 3.1 3.1 2.8 7.6 7.3 7.1 6.7 6.0 3.0 3.7 2.8 2.8 2.8 No. 6 X-ot P 3.6 5.8 ' 8.6 11.0 18.2 26.7 32.1 51.2 61.3 67.8 79.8 81.8 92.0 No. 8 0.9 0.15 3.6 5.8 Av. I. 0. 89.800 91,600 73.300 61,000 59.800 71.700 101,600 19.1 20.9 28.0 28.9 87.8 96.8 88.500 33.000 98.500 85,500 Tine (hr) 1.08 2.58 3.08 8.33 8.58 8.83 5.08 5.33 5.83 6.08 6.53 7.08 ~13- pH 7.5 6.5 5.8 6.0 5.7 5.2 5.0 8.8 8.0 3.3 2.0 2.6 No. 7 5 0: P 2.1 5.0 5.8 28.5 37.8 85.8 53.3 57.9 61.3 62.5 68.8 75.6 Av. H. W. 130,000 119,000 123,000 98,300 98,300 Part B - Nitrogen Atmosphere marinate #9 and #10 ggang 3:; pH 5 of P 0.5 7.5 17.1~ 0.67 7.5 38.1 0.83 7.3 52.6 1.00 7.3 65.6 1.67 7.5 83.1 2.00 8.3 88.7 3.08 7.5 90.5 8.00 6.5 91.2 Experiment #11 0.00 1.00 1.50 1.67 1.83 2.08 2.50 3.75 Potassium pox-sulfate used = 0.8 (0.0023 sole) A's He We 318,000 371,000 382,000 378,000 351,000 319.000 ‘ 309,000 303.000 Time (hr) 0.25 0.75 1.00 1.25 1.50 1.75 2.00 2.25 2.75 3.25 3.75 8.15 Potassium per-sulfate used I 0.3 g. 6.9 6.8 6.3 7.1 7.8 7.6 6.8 7.5 0.62 25.1 39.8 58.1 70.0 87.6 91.1 336,000 378,000 376,000 378,000 353,000 310,000 222.22 pH '5 of P 7.2 1.1 8.0 29.2 7.8 88.8 7.5 55.1 8.0 61.6 8.0 68.8 8.0 “66.5 8.0 66.7 6.2 70.2 5.6 70.9 8.1 88.3 8.1 87.1 (0.0017 :01.) Av. M. W. 319,000 319,000 2.38000 217,000 168,000 Part B - Nitrogen Atmosphere (cont'd.) Experiments #12 and #13 Potassium persulfate used 8 0.2 g. \ (0.0011 mole) .15- {:3 pH 1 of P Av. M. U. :3; 0 pH. 5 of P Av. 11. W. 0.00 8.0 1.00 7.2 1.08 7.6 _ 1.75 7.1 2.5 1.33 7.5 1.8 2.25 7.2 37.8 _ 1.58 7.6 1.8 2.50 7.2 88.2 365,000 1.83 7.5 2.5 2.67 7.11 68.3 2.08 7.11 3.2 3.08 7.6 76.8 335,000 2.33 7.3 I" 5.0 I 3.58 83.1 2483 A 7.8 18.2 138,000 8.00 8.0 88.8 268,000 .3.08 7.3‘ 28.1 208,000 8.55 89.0 3.33 7.6 80.0 230,000 5.58 91.6 271,000 3.58 7.5 53.8 288,000 8.08 7.8 73.6 8.58 7.8 80.0 238,000 5.08 7.8 88.8 230,000 6.00 92.2 ' Part B - flitfiogen Atmosphere (cont'd.) hperinent #18 Potassiun pereulfote used 8 0.1 g. (0.0006 mole) Tine (hr) pH % of P Av. 11. W. 2.03 6.8 2.58 7.1 1.8 3.08 7.1 1.8 3.58 6.8 1.8 8.58' 6.8 5.3 x. 5.08 6.3 7.2 . 5.03 6.8 18.5 86.200 6.08 7.1 23.2 129,500 6.58 6.8 82.8 236,000 7.58 6.6 78.8 275,000 8.08 6.8 88.2 267,000 08...... MEFN \ 0 .0 v m N m k .W - \l - 3e m s \ \.\. \\\.\G.-\QNW.WD °\ 03.60.. a \ 000w... new“. . .\\‘\Nn.w .. . QQV\\0\.\N‘.WN°§N\N‘ *www “N QN \\ \“h‘V \\ QQK w“ Nfihu /0 \ sewn.» 0.\m.nu omua 0%..3 . 0 . \ \ 7 00m nu \. 0...... .. 01. A \. 03 we. 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