August 1949
INDUSTRIAL AND ENGINEERING CHEMISTRY ACKNOWLEDGMENT
7
The authors wish to acknowledge the assistance of ArcherDaniels-Midland Company, Minneapolis, Minn., and the Werner G. Smith Company, Cleveland, Ohio, who cooperated with others previously acknowledged (IO) in the production of Sorepol on a commercial scale in 1942 to 1943. The Standard Oil Development Company, Witco Chemical Company, Procter & Gamble Company, and Chrysler Corporation assisted in the evaluation of rubber sa.mples. The authors are also indebted to the Standard Oil Development Company and to the Petroleum Refining Laboratory, School of Chemistry and Physics, Pennsylvania State College, for furnishing samples of lubricating and hydraulic oils, and certain hydrocarbon polymers. The authors are indebted t o R. H. Manley, former Division Head, Oil and Protein Division, Northern Regional Research Laboratory, for his guidance and leadership during 1942, and to W. J. Sparks of Standard Oil Development Company and W. C. Ault of the Eastern Regional Research Laboratory for their interest and suggestions. LITERATURE CITED
(1) -idkins, Homer, “Reactions of Hydrogen with Organic Com-
pounds Over Copper-Chromium Oxide and Nickel Catalysts,” pp. 13, 20, Univ. of Wisconsin Press, 1937. ( 2 ) Bradley, T. F., and Johnston, W. B., IKD. ENG.CHEM., 32, 802 (1 ~ 4 n 1
(3) Ibii.: 33,.86 (1941). (4) Carothers, W. H., I b i d . , 26, 30 (1934). ( 5 ) Carothers, W. H., and Hill, J. W., J. Am. Chem. Sac., 54, 1559 (1932). (6) Ibid., 1566, 1579 (1932). (7) Carothers, W. H., and Van Natta, 11’.J . ,Ibid, 55, 4714 (1933). (8) Committee on Analysis of Commercial Fats and oil?, AM. CHEM. SOC., IND. ENG. CHEM., 18, 1346 (1926). (9) Cowan, J. C., and Ault, W. C., U. S. Patent 2,373,015 (1945). (10, Cowan, J. C., Ault, W.C., andTeeter, H. M., IND. ENG.CHEM., 38, 1138 (1946)
1653
( 1 1 ) rowan, J. C., Falkenburg, L. B., and Teeter, H. M., IND. ENQ. CHEM., ANAL.ED., 16, 90 (1944). (12) Cowan, J. C., Lewis, A. J., and Falkenburg, L. B., Oil & Soap, 21, 101 (1944). (13) Cowan, J. C., nnd Teeter, H. M., U. S. Patent 2,384,443 (1945). (14) Cowan, J. C., and Wheeler, D. W., J . Am. Chem. SOC., 66, 84 119441. --, \ - -
U. S.Patent 2,429,219 (1947). (16) Earle, F. R., and Milner, R. T., Oil & S o a p , 16, 228 (1939). (17) Eckey, E. W., andTaylor, J. E., U. S.Patent 2,413,612 (1946). (18) Evans, H. C., and Young, D. W., IND. ENG.CHEM.,39, 1676 ( I 947). (19) Flory, P. J., J . Am. Chem. Sac., 62, 1057 (1940). (20) Frosch, C. J., U. S. Patent 2,388,318 (1945). (21) Goebel, C. G., J . Am. Oil Chemists’ Sac., 25, 65 (1947). ENG.CHEM., 29,968 (1937). (22) Hickman, K. C., IND. (23) Hoffman, H. D., and Green, C. E., OiE & Soap, 16, 236 (1939). (24) Howard, J. B., U. S. Patent 2,410,073 (1946). (25) Johnston, W. B., U. S. Patent 2,347,562 (1944). (26) Kass, J. P., Norris, F. A., and Burr, G. O., paper presented before Division of Paint and Varnish Chemistry at the 99th Meeting of the AMERICAN CHEMICAL SOCIETY, Cincinnati, (1.5) Ibid.,
Ohio. (27) Kaufmann, H. P., “Studien auf dem Fettgebiet,” p . 23, Berlin, Verlag Chemie, 1935. (28) Mark, H., IND. ENG.CHEM.,34, 1343 (1942). (29) Mrhlenbacher, V. C., Official and Tentative Methods, 2nd ed., Am. Oil Chemists’ Soc., Official Method Cd 1-25. (30) Ross, J., Gebhart, A. I., and Gerecht, J. F., J . Am. Chem. Sac., 68, 1273 (1946). (31) Shriner, R. L., Home, W. H., a n d Cox, R. F. B.. “Organic Syntheses,” Collective Vol. IT, p. 453, edited by A . H. Blatt, New York, John Wiley & Sons, 1943. (32) Sparks, W. J., and Young, D. W., U. S. Patent 2,424,588 (1947). (33) Teeter, H. M., Scholfield, C. R., and Cowan, J. C., Oil & Soap, 23, 216 (1946). (34) Wnterman, H. I., and Van Voldrop, C., Alien Property Custodian, Patent Application 359,978 (filed 1940). (35) Whitely, J. M., Jr., and Turner, L. B., U. S. Patent 2,260,117 (1942). RECEIVED February 7, 1947.
DIGLYCOLIC ACID A New Commercial Dibasic Acid IT. M. BRUNER
AND L. T. SHERWOOD, JK.
A m m o n i a D e p a r t m e n t , E. I . du Pont d e Nemours 6% C o m p a n y , Tnc., W i l m i n g t o n , Del.
D
Diglycolic acid is now available for the first time on a commercial scale. -4s an oxygen-linked, dibasic acid it provides industry with a new raw material of many potentialities. Diglycolic acid is a white, odorless, relatively nonhygroscopic, crystalline product which can be packaged and used as a solid. It is intermediate in strength between acetic acid and oxalic acid. Over a wide range of conditions it shows good chemical stability. It can be esterified by direct methods or by alcohol exchange. The anhydride, acid chloride, amide, salts, and many other derivatives can be prepared by familiar techniques. Of these derivatives the esters appear to be most interesting, and some are expected to help fill the present need for more plasticizers. Some toxic effects of the methyl and ethyl ester have been observed, but experience has shown that both these materials are safe to handle if proper precautions are exercised.
IGLYCOLIC acid is a n oxygen-linked, dibasic acid formerly unavailable to the chemical industry, but now for the first time it is being manufactured on a commercial scale by the -kinmonia Department of E. I. du Pont de Nemours & Company. As a laboratory chemical diglycolic acid has been known for many years ( 1 7 ) . It was known to possess versatile reactivity forming esters, amides, salts, anhydrides, and other derivatives. B study of the properties of these materials suggests that the acid should be valuable in a number of applications, particularly as an intermediate to plasticizers. PHYSICAL PROPERTIES
Pure diglycolic acid is a white, odorless solid, having the formula IIOOCCH~OCH&OOH. The monohydrate is formed a t 25 C. on exposure to relative humidities above 72y0. The pure, anhydrous acid gives a hard, strong pellet on pressing in a die. The commercial product, which is anhydrous, is a white, free-flowing, flaky material. Diglycolic acid is somewhat stronger than acetic acid and weaker than oxalic acid. At 25 C. the p H of aqueous solutions ranges from 1.36 to 2.08 as the concentration is changed from 1 0 . O ~ oto 0.5%. Other properties are given in Table I. Be-
I N D U S T R I A L AND E N G I N E E R I N G CHEMISTRY
1654
TABLE1. PHYSICAL PROPERTIES OF DIGLYCOLIC ACID A N D ADIPICACID Diglycolic Acid hIrltiniI point Solut>ility
c.
00 2.3' C.
Ionization cons t a n t ? a t 25' C. Crvsralline form Hygroscopicity Fln-h F1a.h .-
n o ~.~ int point (Clevrl In d (Cleveland open cup) Fire point poi] (Cleveland open cup) c ~
.Idipic Acid
lfron1 water) Sonhygroscopic a t rcle til-e humidity
50%
152.10 C . 0.3 e . . 100 g. IS20 at 01 2 . 5 & / l o 0 g . H?O a t 25' C. Sol. in ethanol Insol. i n e t h r r ki = 3.7 X 10-5 k? = 2.4 X 10-6 llonoclinic urisms !from water) Nonhygroscopio a t 50% relative hiiinidity
c.
~~
440' F. 445O
F.
4100
F.
cause adipic acid is a close technical relative! values for it are giren CHEMICAL REACTIONS
STABILITY.Diglycolic acid is a relatively stable compound. Tests show that hydrolysis does not occur rapidly with 2 to 2.S70 sulfuric acid a t 200" C. Treatment with n-ater for 3 hours a t 225' C. gives a 1%:conversion to hydroxyacetic acid, vihercas zinc chloride solutions under the same conditions increase hydrolysis to only 49& Methanol does not appear to at,tack the oxygen linkage. When treated LTith methanol for 2 hours a t 225" C., diglycolic acid or its methyl ester produces only traces of hydroxyacctic acid and methoxyacet'ic acid. Some discoloration takes place wlien aqueous solutions of diglycolic acid are refluxed. The same effect is noted a i t h the molten acid in contact with air. I n a dilute aqueous solution potassium dichromate does not osidize diglycolic acid when the mixture is boiled during 1 hour. Dimethyl diglycolate and niany higher esters shox fair thermal stability at 200' to 225' C. On pyrolysis a t atmospheric pressure diylycolic acid is reported to decon-pose to hydroxyacetic acid, polyoxymethylene, carbon monoxide, and carbon dioxide ( 1 1 ) . Pyrolysis of thc anlib-dride at 450" to 500" C. yields maleic anhydride and some ketene (19). When diglycolic acid is heated v-ith potassium hydroxide, oxalic and acetic acids are formed (15). Heating the calcium salt with sulfuric acid gives carbon monoxide and polyosyinethylcne ( I S ) . Decomposit,ion also occurs when the acid is heated with various strong acids. Fuming hydrochloric acid a t 120" C. converts it to hydrosyacetic acid. Similar treatment with hydriodic acid reduces the hydroxyacetic acid first fornied and yields acetic acid (12).
SALTFORAIATION. Diglycolic acid forins salts in much the same manner as other dibasic acids. Salts of the allmli metals, the allraline earth metals, and some of the heavy metals have been reported in the literature (9, 26-18, 83). Of special interest is the low solubility of the sodium and potassium acid sails as compared n-ith the free acid and the completely neutralized salts. Tests show the following solubilities uf these diglycolates : Solubilitr ( G . '100 G . 1 1 2 0 ) 00
c.
20.9 2 6 1.5 72.0 168.0
methods: (1) by the action of 1 mole of acet,yl chloride on diglycolic acid, ( 2 ) by distillation of the acid a t 11 to 12 mm., and (3) by the reaction of 1 mole each of phosphorus pentachloride and diglycolic acid in a chloroform solution. ACID CHLORIDEFoRiraTIoN. Diglycolyl chloride may bo formed by the action of 2 moles of phosphorus pentachloride on 1 mole of diglycolic acid ( 5 ) or by the addition of carbon monoxide to dichloromethyl ether in t,he presence of a Friedel-Crafts catalyst (25). ClCHzOCHsCl Dichloromethyl &her
+
--+
2C0 Carbon monoxide
O(CH2COCl)Z Diglycolyl chloridc
REDCCTION.Work in these laboratories has shown that dimethyl diglycolate is a source of diethylene glycol in high yields via hydrogenation.
45OC F.
for comparison.
Diglycolate Dig!ycolic acid Sodium hydrogen diglycolate Potassium hydrogen diglycolate Sodium diglycolate Potassium diglyrolate
Vol. 41, No. 8
250
c.
71.5 5.1 3.4 88.0 188 0
AXHYD-KIDE FO-KAL~TI~S. Slany derivatives of diglycolic acid can be made by way of t h e anhydride or the acid chloride. In these laboratories the anhydride \vas prepared in 91Yb yield b y the reaction of diglycolic acid and acet,ic anhydride. I t is a white crystalline solid ivhich melts at 97" C. and boils at 120" C. a t 12 nini. I n the presence of water it is readily convcrt.ed to diylycolic acid. .4nschbtz (4,5) had previously synthesized it by three
+
O(CH,COOCHa), 2H2 + O(CH,CHzOH), Dimethyl Hydrogen Diethylene diglycolatc glycol
+
2CHxOII Methanol
ESTERIFICSTIOX.The most important cheniical reaction of diglycolic acid from the commercial point of vien- is esterification. Using direct esterification wit,h standard techniques a wide variety of est,ers has been prepared in the presence of sulfuric acid catalyst. When the use of an acidic catalyst is not permissible, as when the alcohol contains a n acetal linkage, an exchange between the alcohol and dimethyl diglycolate may be used. In this mandiglycolate has been prepared ner di [2-(methox~~methoxy)ethyl] from 2-(methosymet~hoxy)ethanoland dimethyl diglycolate. The boiling points and refractive indexes of a few esters synthesized by these methods are given in Table 11.
TABLE11. BOILISGPOIXTSAND REFRACTIVE INDEXES 06 ESTERS Boiling
' C./Mm. Point,
Ester Di-n-butyl diglycolate Di [2-(2-butoxyethoxy)etl1yl] diglyoolate Dicvrlohexvl dinlvrolate Di-n-decyl "diglFchate Didecyl diglycolate (from branched chain alcohols) Di(l.3-dimethylbutyl) diglycolatr Diethyl diglycolate Di(2-ethylhesyl) diglycolate Diisobutyl diglycolate Diiaopropyl dialrcolate Dimethyl diglycolate
157/7 224/2 185/4 226/1 220/1 158/3 130/20 200/5
113/1 123/7 139/30
Refrartire Index, "2: 1.4328 1,4466 1,4723 1.4461 1.4501 1.4326 1,4240 1.4442 1.4288
1.4220 Solid, I C 0 n m.g UY
190/2,5
17.515
Di-n-octyl diglyoolate Dianiyl diglycolate (from mixed amyl alcohols) Di-n-propyl diglycolate Di(tetrahydrofurfury1) diglycolate Di(3,9,5-trimethylhexyl)rliglycolat,e Di-n-biitvl Dhthalate Diethyl phihalate Di(2-ethylhexyl) phthalate Dimethyl phthalate Di(3,~,5-trim~tliylllexylj phtlialate
168/4 270/5 136/0.5 122/2.5 162/4 200/3 182/5 141,'s 229/5 132/5 202/2
".
1 ,4428 1.4417 1,4373 1.4421 1,4352 1,4290 1,4558 1.4451 1 ,4805 1.5030 1 ,4800 1,5155
1 ,4800
Other niet,hods of ester preparation include the reaction of diglycolyl chloride with methanol or ethanol ( 6 ) ,and the action of potassium diglycolate on the active halogen of an a-chloromethyl ether ($4). 2ROCHzC1
+ O(CH2COOK)Z --+ O(CH2COOCHZOR)2 + 2KC1
a-Chloromethyl ether
Pot.assium diglycolat,e
Dialkoxymethyl diglycolate
Potassium chloride
When diglycolic anhydride reacts with an alcohol, an alkyl hydrogen diglycolate is formed. This method has been used t o prepare niethyl hydrogen diglycolate (6). CHIOH Methanol
+
O(CHr,C0)20 Diglycolic anhydride
+
CH~OOCCHzOCHzCOOH
Nethyl hydrogen diglycnlate
INDUSTRIAL AND ENGINEERING CHEMISTRY
August 1949
Another type of esterification is the synthesis of aromatic esters by the action of diglycolyl chloride on phenol derivatives in the presence of a base. Processes for making diglycolates of the following phenols have been patented: phenol, salicylic acid, anaphthol, p-naphthol, guaiacol, a-cresol, p-cresol, o-chlorophenol, p-chlorophenol, o-nitrophenol, and p-nitrophenol ( 1 ) . AMIDATION.Diglycolic acid derivatives are easily converted to amides. Diglycolamide may be formed by the action of alcoholic ammonia on esters of diglycolic acid (14). Heat converts it to the imide by the elimination of ammonia. At 100' C. water hydrolyzes one amide group to the acid. I n other respects, the behavior of diglycolamide is normal. One derivative, N-benzyldiglycolamide, is useful in the identification of the acyl group of diglycolates (8). Diglycolic acid also forms substituted cyclic imides of interest (66). The elimination of water from the acid amine salt and the vacuum distillation of the product has given a number of N-alkyl diglycolimides.
HOOCCHzOCHzCOONHnRt
+0
\
NR
\
/
+ 2Hz0
'CH9C6 Alkylammonium hydrogen diglycolate
AT-Alkyl diglycolimide
\o
/
\CH&O Diglycolic anhydi ide
CBH,NH, Aniline
'
HOOCCHzOCH?CONHCsHj Diglycolanilic acid
CHiCOCl Acetyl chloride
O(CHaC0)2NGHn I\--Phenyldigly colimide
Dimethyl diglycolate
3,4-Diphenylfuran-2,5dicarboxylic acid
In a similar way dimethyl diglycolate may be oonverted to the brnaylidene derivative by treatment with benzaldehyde.
13(?llznlclchydl.
Dimethyl diglycolate
Polyvinyl Chlorideb
Plasticizer Di(2-ethylhexyl) diglwolate Di(3,5,5 trimethylhexyl) dlglycolate Di-n-octyl diglycolate Di-n-decyl diglyoolate Didecyl diglycolateg Di[2 (methoxymethoxy)ethyl diglycolate Die yclohexyl diglycolate Di(l,3-dimethylbutyl) diglycolate Di(Loro1-R) diglycolatei
-
C
C
C
C
C
c
C
C
C
C
-
a
CelluCelluPolylose Ace- lose Xistyrene0 tat& trate"
C
C
C
C
c
Ch
..
..C
C Ch
C C
C
C
I
Ethylceiliilose/
C
C a n d I denote compatibility and incompatibility, redpeotively, f o r ester
content indicated. b Blended by milling composition with 331/s% ester, 160" C. 0 Blended by casting films from benzene solution containing 9.1% plasticker a n d 90.9% polystvrene. d Blended b y casting films from acetone solutions containing 20% plasticizer and 80% cellulose acetate. e Blended b y casting films from butyl acetate containing 16.7% idasticiaer rtnd 83.3% nitrocellulose. f Blended b y casting films from toluene-ethanol solutions containing 13% plasticizer rtnd 87% ethyloellulose. 8 From nnxture of CIOalcohols of branched chains. h Exudes slowly. 4 F r o m Lorol-R, mixture of alcohols from hydrogenation of coconut oil.
chloric acid or sodium hydroxide t o 5% sodium hydrogeii tfiglycolate are shown in the following tabulation: pH, 25' C.
Solution
1 mole 1 mole 1 mole 1 mole 1 mole
NaHCaHaOa 0.1 mole NaHCaHaOa NaHCpH40s f 0.2 mole NaHCaHaOa 0.1 mole NaHCaHaOa 0.2 mole
+
HCI
+ +
NaOH NaOH
HCI
3.35 3.20 3.08 3.42 3 , .55
Under the same conditions, a 570diglycolic acid solution has a p l l of 1.71. The sodium salt is expected to be of interest as a masking af:ent for use in leather tanning. The literature reports that, Sbenzylthiuronium diglycolate, [C~HF,CHZSC(--NHZ)(=NH,) I ZO(CHsCOO-)Z, is of value as a derivative for the identification of the diglycolate ion ( I O ) . ESTERS. Diglycolic acid is of greatest interest as an intermediate to esters which are expected to be of value in many applications. The higher esters are effective plasticizers for several polymeric substances including polyvinyl chloride, polystyrene, polyvinyl acetals, and cellulose derivatives. These esters are easily incorporated into the polymer by milling or solvent casting. They have a high degree of compatibility, and impart good flexibility and low temperature, properties. Table I11 lists the compatibilities c~H~---c~H, of a number of diglycolates with polyvinyl chloride, polystyrene, cellulose (3COOH acetate, nitrocellulose, and ethylcellu0 lose. 3,4-Diphenylfuran-2Table I V shows t h a t the use of diglycarboxylic acid colates gave -polvvinvl - chloride comDositions of low brittleness temperatures. Samples containing 331/3% of di(2-ethylhexyl) diglycolate, di-noctyl diglycolate, and di-n-decyl diglycolate gave values lower than that of the control, di(2-ethylhexyl) phthalate. The value for di(3,5,5-trimethylhexyl)diglycolate was about the same as that of the control. Table IV also shows the excellent flexibility imparted to polyvinyl chloride by several esters at 331/370content. The stiffness of the polyvinyl chloride films containing the diglycolates of 2-cthylhexanol, n-octanol, 2-(methoxymethosyj ethanol, and isobutyl alcohol was less than or equal to that for the film containing di(2-ethylhexyl) phthalate. The film containing di-n-decyl diglycolate from straight-chain alcohols was somewhat stiffer. Tensile strengths for the above plasticizers werc about +
I n this way derivatives of a-, rn-, and p-toluidine and other aryl amines were prepared. OTHERREACTIONS.The versatility of diglycolic acid and its derivatives is further exemplified by the conversion of the dimethyl ester to furan derivatives. When dimethyl diglycolate is condensed with benzil in the presence of sodium methoxide and methanol, a mixture of 3,4-diphenylfuran-2-carboxylic acid and 3.4-diphenylfuran-2,5-dicarboxylic acid is formed ( 7 ) .
Bend
TABLE111. COMPATIBILITY OF DIGLYCOLATE ESTERSWITH VARIOUSRESINS"
Water
These derivatives are characterized by a very sweet taste, are hygroscopic, and are rapidly hydrolyzed. iV-Aryl diglycolimides have also been prepared by similar methods (5, 6). The action of diglycolic anhydride on aniline converts it to diglycolanilic acid, which may be converted to the corresponding diglycolimide by acetyl chloride.
0
165%
Dibenxylidenc- Water diglycolic acid
S.4~1'6. \T'ork 111 these laboiatories has shown that sodium hydrogcn diglycolate may have value as a buffer for pH control in chemical reactions. Changes of p l l on addition of 0.5 S hydro-
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
1656
TABLE IV. PROPERTIES OE’Pr.as~rcrzsnPOLITISYI, CHLORIDE^
%
Brrengt!i, Lb./Scl. Inch
1050
378
2460
Stiffnesnd, Lb./Sq. Inch 10s.;
1 ,500 142,i
157.3 13.50
352 262 320 X72
213,/ Inch
ngation
TerisileC
Ev~da-
Geon 101, containing 4 % basic lead carbonate stabilizer. . I . S . T . X Designation D 746-43T. Designation D 4 1 2 4 1 , die C, speed 20 inches per Tensile ytrength a t breaking point (.i.S.T,II. iiiinute). .i Stiffness a s measured b5- .i.S.T.LI. standards with Tinius-Olsen stiffness tester (.LB,T.II, Desienation D 747-43T, span 0.5 inch, apec,iiiion diinensions 1 X 0.5 X 0.075 * 0.01 inch). e .It 30% relative humidity a n d 23O C . for a t least 3 months. i F r o m mixture of CIOalcohol., of bsanched chains. a From Lorol-R. mixture of alcohols f r o n i h y d r o ~ ~ n a t i oofn cocon:it oil. b
C
-4s
72.5
415
2075
860
1\ one
- 30 - 47
- 52
3oa 306 400 410
2200 2073 2126 2125
870 708 878 872
Sone None
- 40
873 973 875 82.5
-41 T8
1050 1100
341 302
2475 2150
Q65 1244
IIuch Xorie
- 22 -35
102.5
298 375
2325 2100
1045
Sone None
1050
cxquivalent to that for t,he control. Trsts in this laboratory have 6hoa.n that the diglycolates are generally slightly more volatile than the corresponding phthalates, as Jvould be expectd from the boiling points shown in Table 11. Similar information for 385; plasticizer in polyvinyl chloridp is given in Table I-. The polyester from ethylene glycol and diglycolic acid was foiind to he conipatihle with ccllulose acet,atc, perhaps hecausc of the oxygen linkage. It was not compatible with polyvinyl cliloridc and nitrocellulose. Sovel types of plasticizers for resins such as polyviriyl acetals have been claimed in the patent literature ( 2 1 ) v-here diglycolic acid may bo used in mixed esters of the foilon-iiig type: ROOCCH,0CHeCOOCR2COOR’. Monomeric esters in other applications include quinine diglycolate ( 2 ) . This was preparctl by several esterification procedures and was patented as a tasteless quinine derivative particularly as its sulfate, C?H4Oa(C,,H,,O,r;,),.H,SO,.3H,O. The acet,al esters, (ROC€€,OOCCH:),O, liave been patented as water repellent,s for fabrics when R is an alkyl radical of at) least twelve carbons (26). Polynierized esters of unsaturated alcohols should be useful as resinous coatings and lo\\- pressure laminating resins. Polymeric diallyl diglycolate and a process for making it have been patented ( 3 ) . A process for agglutinating fibrous materials such as layers of pnper with condensation products of diglycolic acid and polyhydric alcohols has been patented (SO). The products are hardened under pressure and are said to he uscful as rcsinous materials. Other polymeric materials may be obtained by tlit: action of
’3 50
diglycolic anhydride on regeneratedcellulose and cellulose acetate in the presence of tcrtiary amines. It i s claimed that these derivatives may be cast into sherats arid may be tilcnded into lacquers and adhcsivrs ( 2 2 ) .
tion8 Yone
a
Di(2-erhylhexyl) diglycolate Di(3,5,5-trimethylhexyl) diglycolate Di-n-ootul di,glycolatc Di-n-decyi diglycolate Didecyl diglycolatej Di[2 - (niethoxymethoxj7)ethyl] diplycolate Dicyclohexyl diglycolatr Di(l.3-dimethvlbutvl) diglycolate ” ” Di(2-ethylhexyl) phthalate a Footnotes as in Table I V .
Vol. 41, No. 8
Sone
Sono
PHYSIOLOGIC.LL EFFECTS O F
RS
111 those situations here mists and vapors of certain ot thc lower esters may be encountered a word of warning is in order. Tests conducted by D u Pont’s Haskell Laboratory of Industrial Toxicology showed that exposure of the eyes to dimethyl, diethyl, and di(2niethoxyethyl) diglycolates caused a corneal cloudiness resulting in temporary blurring of vision. This condition was not preceded by any waming, as the ester vapors did not irritatc thc rye. Following a single exposure the condition was teniporary only, and normal vision returned in 48 to 72 hours. The eilfects of repeated exposures are not Bnown. They were most, pronounced in the case of the dimethyl and diethyl e s t e r s, Dipropyl, diisopropyl, di-nbutyl, diisobutyl, and diallyl diglycolates did not show this effect. Experience in both the plant and laboratory has shown that esters may be handled without danger if proper precautions are observed.
LITERATURE CITED
(1) Ach, L., Ger. Patents 223,305 (May 30, 1910); 236.045 (June 6, 1911); C. S. Patent 948,084 (Feb. 1, 1910). (2) I h i d . , 1,032,642 (July 16, 1912). Adelson, D. E., and Dannenberg, H., I h i d . , 2,386,999( O m . 16, 1945). Bnschutz, R.. Ann., 259, 187 (1890). Anschtitz, R., and Biernaux, F., Ibid., 273, 64 (1893). Anschtltz, R., and Jaeger, S . , Ber., 55B,670 (1922). Backer, H.J., and Stevens, W., Rec. trav. chim., 59, 423 (1040). Dermer, 0 . C.,and King, J., J . Org. Chem., 8 , 168 (1943). Donk, M.A. D., Rec. traa. chim., 26,214 (1907). Donleavy, J. J., J . Am. Chem. Soc.. 58,1004 (1938). Heinta, W., Ann., 128, 129 (1863). Ihid.. 130,267 (1864). I h i d . , 138,40 (1886). Ihid.. 144.91 118671. Heinta, ‘CT’ , Ann Physak, 109,471 (lS80i I h i d , 115,280 (1562). I h i d . , 115, 462 (1862). Heinta, W., J . Chem. Soc.. 1859,363. I-Iurd. C . D., and Gla-n. H. E . , J . Ana. Chem. S o c . , 61, 3490 (1 939). I. G. Farben, French Patent 694,941 (Dec. 12, 1930:. K y r i d e s , L. P., U. 8. Patents 2,073,937 (March 16.1937): 2,073,938 (March 16. 1937); 2.120,755(June 14, 1938); 2,120,756 (June 14, 1935); 2,205,420 ( J u n e 26, 1940): 2,331,328(Oct. 12, 1943). Malm, C . J., and l o i d y c e . C . It.,I b i d . , 2,024.238(Der. 17, 1O33. hIohs, R., 2. C h e m , 9,498 (1886). Rosenbach, J., and Balle, G.. IJ. 8 . Patent 2,283,784( J l a y 19,
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RECKIYED September 2 2 , 1048. I’rsaenred b?fore t h e Division of Indiistrial and EnRinwring ChemistrJ- a t 1111, l l 4 t l i ZIeeting of the .IVERIF 1s C ~ F : \ I I C A L SOLIETY, S t . Louis, hlo.
