Document baBM6bpgpVZB3E9QJ11Bg3eeo

Ciro.: Associate and Asr,*.. want Research Directors St. Louis Research Report No. 1184 Copy No. 5 /-s FINAL REPORT ALKYLATION OF AROCLORS FOR EVALUATION AS EXTENDER PLASTICIZERS Job No. 2-02-750.01-2682 (Work done by Phosphate Research under Anniston Job No. 171-1042) Monsanto Chemical Company Organic Chemicals Division St. Louis Research Department Date: January 17, 1955 Work done by: Prepared by: W. W. Marshall A. M. Ellenburg D. H. Chadwick W. W. Marshall 0690A20 HARTOLDMONOOQ5126 Eleven copies of the Final Report for ALKYLATION OF AR0CL0R3 POR EVALUATION AS EXTENDER PLASTICIZERS, Job No. 2-02-750.01-2682(Work done by Phosphate Research under Anniston Job No. 171-1042), prepared by W. W. Marshall, dated January 17, 1955, have been distributed ns follows: 1. File 2. D. H. Chadwick 5. H. K. Nason - file 4. Duplicate File 5. Circ: Associate and Assistant Res. Directors 6. A. M. Ellenberg 7. J. R. Darby 8. England (event.) 9. England (event.) 10. Extra 11. Extra This report contains confidential Information which is the property of the Monsanto Chemical Company and which shall be disclosed only to duly authorized persons. The recipient is held accountable for the filing and safe custody of the report, which must be returned on demand. 0690421 HARTOLDMONOOQ5127 TABLE 0 F CONTENTS I. II. III. IV. V. VI. VII. Page No. INTRODUCTION.......................... 1 SUMMARY..................................................................................... 1 CONCLUSIONS ............................................................................ 1 RECOMMENDATIONS ................. ................................................. 2 REFERENCES TO PREVIOUS WORK........................................ 2 EXPERIMENTAL DATA............................................................... 5 DISCUSSION OF RESULTS ...................................................... 4 0690A22 I HARTOLDMONOOQ5128 INTRODUCTION 1. It was desired to develop an Inexpensive plasticizer for use as a plasticizer extender with polyvinyl chloride. HB-40 Is presently used as plasticizer extender, however, it has a rsther high volatlllt.', It discolors on exposure to ultraviolet 11;,..c and the supply a: a low price is limited. Aroclors could be made available in almost unlimited quantities, but have an objectionable odor when used as plasticizers. It was Intended to attempt to develop a plasticizer by the alkylation of a low molecular weight Aroclor which would be competitive in price with HB-40 but with lower volatility, cf good color stability and without -in objectionable odor. II. SUMMARY Aroclors 1232, 1242 and 1248 were successfully alkylated, as described in Table I, with n-butyl chloride. Isopropyl chloride and propylene, using aluminum chloride as the catalyst. A yield of 73-5$ was obtained when Aroclor 1232 was alkylated with n-butyl chloride whereas yields of 86.0$ and 74.5$> respectively, were obtained when Aroclors 1242 and 1248 were alkylated with Isopropyl chloride. Respective yields of 81.5$ and 83.0$ were obtained when Aroclors 1242 and 1248 were alkylated with propylene. Yields of less than 20$ were obtained when the alkylation was attempted with various amyl chlorides / a large amount of the amyl chloride was recovered as amylene. Attempts to alkylate various Aroclors with tripropylene and with Isobutylene failed when aluminum chloride and various boron trifluoride complexes were used as catalysts. The alkylated Aroclor was compared with HB-40 as a plasticizer extender at the Organic Division Research Department. The alkylated Aroclor was slightly less volatile than HB-40 but also less flexlbilizing. The balance of properties made them quite similar in plasticizer value; however, the high specific gravity of the alkylated Aroclor made it less valuable than HB-40 on a volume basis. Surprisingly, the light stability of the alkylated Aroclor was inferior to HB-40, both in stabilized and unstabilized poly vinyl chloride compositions and by direct exposure of the alkylated Aroclor to ultraviolet light. III. CONCLUSIONS From this experimental work it is concluded that Aroclors 1221, 1232, 1242 and 1248 can be alkylated with propylene, isopropyl chloride and n-butyl chloride in yields of over 70$. Further study would probably permit definition of conditions to give maximum yields ; however, this work would not be Justified on the basis of product evaluation. 0690423 HARTOLDMONOOQ5129 2 It Is also concluded that Aroclor 1242 cannot be all<ylated with amyl chloride under the conditions used as the amyl chloride decomposes to amylene. (yields of alkylated product were less than 20$) Aroclors could not be alkylated with isobutylene or tripropylene as these compounds tended to polymerize under the conditions used. The alkylated Aroclors which were prepared were not suffi ciently light stable to be used as an extender plastlcier in polyvinyl chloride compositions. In addition, these compounds tended to bleed from the plasticized polyvinyl chloride. The specific gravity of the alkylated Aroclor was sufficiently high so as to make them less valuable on a volume basis than HB-40 when used as plasticizers. IV. RECOMMENDATIONS No further work toward developing alkylated Aroclors as substitutes for HB-40 is indicated. V. REFERENCES TO PREVIOUS WORK 1. Phosphate Research Report No. 2042, "Alkylated Biphenyls", Dec. 31, 1945, D. W. Cheape, Jr. 2. Procedure for sample Preparation for Alkylated Biphenyls, Phosphate Division, July 11, 1946, D. W. Cheape, Jr. 3. Phosphate Research Report No. 2129, "Pilot Plant Produc tion of Alkylated Biphenyls", Sept. 12, 1947, C. D. Wood, Jr. 4. Phosphate Research Report No. 2281, "Preparation of Alkylchloroblphenyls", Dec. 1948, R. L. Wolf. 5. Central Research Report (Job No. 4015), June 21, 1943, J. S. Butler 6. Phosphate Division Report No. 2809, "Color Stability of HB-40", Oct. 24, 1952, J. K. Sears. 0690424 HARTOLDMONOOQ5130 3. VI. EXPERIMENTAL DATA: NB 81151-81200 84851-84859 Into a three-necked flask equipped with thermometer, stirrer, and dry ice condenser was charged 1034.0 g. (4 moles) Aroclor 1242 and 50.0 g. (0.225 moles) of aluminum chloride and the mixture was heated to 80* C. while 377 g. (48 moles) of isopropyl chloride was added over a period of two hours. The temperature was held ac 80 C. for one hour after the addition was completed. The reaction product while hot was poured Into 2 liters of cold water, separated and then washed with one-liter portions of water until the washes were neutral. The crude product was then heated to 120 C. to remove water and then treated with dry Attapulgus earth and filtered while still hot. The crude was then vacuum distilled and the fraction distilling at 150-185 C. at 1.5 mm Hg was taken as the product. By total chlorine analysis it was determined that this product was essentially monoalkylated Aroclor 1242. (See Table I). In cases where gaseous alkylating agents such as isobutylene and propyylene were used, the gas was introduced below the surface of the reaction mixture by means of a sparger. Treatment of the reaction mixture was essentially the same as described above. Reaction conditions, yields, etc. are tabulated in Table I. The alkylated Aroclor 1242 prepared in Run No. 2J was compared with HB-40 as a coplasticizer for polyvinyl chloride by Mr. J. R. Darby of the Organic Division Research Department at St. Louis. Both plasticizers are incompatible when used alone, and therefore were evaluated as coplasticizers with dioctyl phthalate. The alkylated Aroclor was slightly less volatile than HB-40 but also less flexibillzing. The balance of properties made them quite similar in plasticizer value; however, the high specific gravity of the alkylated Aroclor makes it less valuable than HB-40 on a volume basis. Surprisingly, the light stability of the alkylated Aroclor in a polyvinyl chloride composition was inferior to HB-40 in both stabilized and unstablllzed compositions. Plasticizer evaluation data are given in Table II. Bieedlng of the alkylated Aroclor from the polyvinyl chloride composition was noted after several months; this did not occur in the HB-40 coplasticized samples. 0690425 HARTOLDMONOOQ5131 Light stability tests on some alkylated Aroclors as compared to HB-40 were run by J. K. Sears, as described in reference 6: Substance Qardner Color after exposure to O.E. sun lamp for___ hours HB-40 lsopropylated 1248 (Run 20) isopropylated 1242 (Run 2(5) mono butylated 1232(Run 17) di butylated 1232 (Run 17) 0 Water White 1 3 7 h2 6 5 7 6 10 84 7 9 9 9 11 lg6 8 n 9+ 12 168 9 Prom this data it appears that the alkylated Aroclors are somewhat less light stable than HB-40. An interesting observation on the alkylated Aroclors which were stored in indirect light in the laboratory was that after several weeks alkylated Aroclors prepared using olefin alkylating agents darkened considerably, whereas those prepared using alkyl chloride alkylating agents did not appear to change color. This discoloration was probably due to a trace of olefinlc impurities in the products, which easily oxidize in the presence of ultra violet light to give highly-colored products. VII.DISCUSSION OF RESULTS It was found that Aroclors 1232 and 1242 could be readily alkylated with alkyl chlorides. The resulting yields of alkylated Aroclors decreased, however, as the length of the alkyl chloride chain increased. This was probably due to the fact that Aroclors are difficult to alkylate and in the case of amyl chlorides the amyl chloride was more readily decomposed to amylene during the reaction, which did not readily react with the Aroclor. Aroclors 1242 and 1248 were easily alkylated in good yields with propylene, whereas low yields were obtained when isobutylene and tripropylene were used. This was probably due to the ease with which isobutylene and tripropylene are polymerized by acid catalysts of the aluminum chloride type. Anhydrous hydrogen chloride was used as a promoter with olefin alkylating agents; it was not determined that it improved the yields. 0690426 HARTOLDMONOOQ5132 Further study would probably permit definition of conditions to give higher yields as Indicated by comparison of Runs 27 and 29, Table I, however this work is not Justified on the basis of product evaluation. The alkylated Aroclors made from olefins became highly colored on prolonged exposure to subdued light whereas the alkylated Aroclors prepared with alkyl chlorides did not show this tendency. This is probably due to traces of olefins in the alkylated product which are easily oxidized to form highly-colored products. rch 3-19-55 W. W. Marshall 0690427 HARTOLDMONOOQ5133 Raw Material! 1\ sI I <2 I| 33 e. SS n s* TABLE I ALKYLATION OP ABOCLORS Reaction ---U Yield,baaed on Aroclo:" Charged I ri JOOH f>Ot> Eg I12*3' Aids 1221 BP* * Pheno' 1221 BP, i rther 1221 ' A .Cl, 1221 , MCI, 12J2(pp') '1.0 0.057 ; i.o. 0.105 0.070 ,12..60|, ] 1I _o.o^ 0.0"5 :*^..o6ll 95 1+1 ` 0.0 0.0 0.0 An undlotillable tarry material was obtained A small amount or alkylated material at tained} most of Isobutylene reacted with ltaeli* .polymerised) Reaction temp, too low - no alleviation. /Low yields of highly-colored material fprobably due to polymerization oft}-,e olefin 1252 1252 12J2 1242 1252 1252 1252 HP0e* BPj 12*2 A1C1, ' HC1. 3.0 0.075 2.0 0.0'T5 0.0^5" ' 2.0 0.075 1 " i 2.0 1CH,Ct 2.0 0.0T5 2.<T 0.225 2.0; 0.15 2.0' 0.225 2.A; 150 Atm. A.O 150 " H*..6o;' 11135* i| '" |?.6| 150 : " 3.o! 90 i 1 3.0| 95 | " *.0j 81 j n 185*227 j 1-0-185 *!" - 0.0 2.0J79.5 l".2 9.5 J?5~8 ]?].28 7R * 2* .6 0.0 12.* 33.82 Low yields of hl?hlv'colored material probabl" due to polymerization of olefin. O' 12*6| 1! 1232 i 3: 1**3 1 12*2 12*2 11112222****2222 1122**82 . Trlpropylenl `Isopropyl* 2.0 0.225 - ; 2.0 0.225 - i *.o. 0.225 *.d 90 ul.lj 130 *.8j 170-208 155-lPl ; 151-18* : chloride' i jMlxed may} } * .0 0.225 *.8; 83 " i 1*0-185 . Chlorldo ) :Primary ' Amyl Chloride - 2.0 0.110 2.*, 90 1*2-192 2.0 0.180 '2.*, [ProgylenejHCl | . 2.0. 0.180 ''.2; l^O Isobutylene ] 1 2.0 0.180 :6.3j 1E5 { 2.0 0.180 5-9! 150 1*2-18* ++66..00' 1*3-180 168-200 ! Propylene j ^ 1 2.0 O.lSo ;53' 150 . +*v6..Ov' nu-;o5 1.3 7*.5 1.4 1.6JP6.0 O.9I12.I 2.6 22.9 139.0 7"5 6.7 135.93 76.0 11.9 I38.I5 0.9>1*.*{ 0.9*13.7> 0.9i6*^.5f 12.0 20.* v01.-..y90*7"3O1>...0O5.v.[;' : 8'17.*o...86* 1l1iye79.*...08* 2*.92 Essentially nonoalkylated Aroclor obtained ^25-Acjf of the amyl chloride was recovered /as anylene.Apparently most of tne amyl xchlorlde was dehydrohalogenated to foi~. \amylene. S- intoir* R 11 l.eo.butylen* HC1 } 22.0- 00..118800 1*7..00* 15-0 `+-.0' 15-0-190 0-.9*8^C*0'- 6i.O'11. .0 *0.39 A black tarry solid was obtained. sihenyl ................ _ * I 2.0 0.180 *.2' 120 46.0 i*o-2*o 1.0 As.o' 16.ft a<<.? Product was mixture of mono v onvereton baue$ on total;riel? crsilke'd' a'lkyiated~prMu5Tr"-Bt'ae^.op'Aro`elor c harged' and tased on theory(nefvt.) a^ealp^IafeS "1 rroo number.of moles of chlorine In product. 0690426 HARTOLDMONOOQ5134 TABLE II EVALUATION OF ISOPBOPVL ABOCLOB lPAp AS PLASTICIZERS Hilling Results Fuming Odor Color Molded Sheet Transparency. Mor Color Low Temp. Plex. Volatility 56 Plast. Lost Hardness Before Volatility After Volatility Heat Stability Color after >0 min. at 32A*P. Rating Water Absorption % sol. matter lost % Absorption Kerosene Extraction Incompatible Serloue Exu dation Heavy Strong SI .dlecolored Clear Very alight Lt. Yellow -2. A* 2J.77* 9B Lt. Amber Oood . HB40 20* DOP 2056 Heavy Moderate SI. Discolored Clear Very slight SI. Discolored -24.3^ 28.20j6 84.2 ' 89.7 Amber yajP 0.1J* o.4o* I 11 0 wwC 40<6 Isopropyl Aroelor Heavy Moderate SI. Discolored Clear Very slight SI. Discolored -30.6* 23.5856 Incompatible Serious Exu- Moderate Moderate Lt. Yellow SI. Opaque Very slight Lt. Yellow 12.9* 15.l6i6 79-3 85 97 97.3 Amber Pair 00,4l>4j*| 79.02$ Lt. Amber Good 0.23* 0.29$ 53.9056 Isopropyl Aroelor 1242 (20*) DOP (20*1 Moderate Moderate Moderate SI. Discolored Clear Very slight SI. Dlecolored -20.46. 21.21* 88 91 laoprepyl Aroelor 12-*2 (M.4. --DO? I25.fr Moderate Moderate SI. Discolored Clear Very alight SI. Discolored -25*8* 17.43* 83.6 8a *P-ber Pair -09* *>1* 90.3056 Amber Fair 0.0656 0.30* 82.425* 0690429 HARTOLDMONOOQ5135