...............* x.#iProductand Process Development A section devoted to information on the development of products 'and the processes for making them on any scale with industrial implications, and including economics and market development
%
. . . . . . . . . . . . . . . . . . . . e
LIQUID POLYBUTADIENE W. W. CROUCH
AND
J. A. SHOTTON
Phillips Petroleum Co., Bartlesville, Okla.
T
HE sodium-catalyzed polymerixation of dienes can be made t o yield a variety of products with a wide range of molecular weights depending on the reaction conditions. The preparation of rubbery butadiene-styrene copolymers using finely dispersed sodium catalyst in a hydrocarbon diluent to control the heat of reaction was described in an earlier paper (8). During the course of that work a number of variables were observed to decrease the viscosity of the rubbery polymer. These included 1. Increasing the quantity or decreasing the particle size of
the catalyst 2. Raising the temperature of the reaction 3. Using butadiene alone instead of a butadiene-styrene monomer mixture 4. Using a diluent that is a solvent for the polymer to keep it in solution during the reaction By adjusting all these variables simultaneously in the direction of a less viscous product, a liquid polybutadiene was made ( 8 ) . At the same time the major problem of handling the solid polymer in the reactor was eliminated. The process was adapted to plan operation, and since 1950 liquid polybutadiene has been in production in a semiworks plant a t Borger, Tex. It is presently marketed under the name Butarez liquid polybutadiene. Numerous reports of liquid polymers of butadiene and other monomers are in the literature and patent art. Perhaps the most widely developed liquid polymer is Vigtanex polyisobutylene. This polymer does not have as high unsaturation as liquid polybutadiene and, therefore, does not have the drying and crosslinking properties which account for the major interests in liquid polybutadiene. Liquid polymers and copolymers of butadiene that have been made in highly modified emulsion reactions ( 7 ) and in hydrogen fluoride-catalyzed reactions ( 3 ) are similar in many respects to the sodium-catalyzed product described but in other important properties, particularly the ability to air dry and cure a t elevated temperatures, the products are not identical. A liquid butadiene polymer, Plastikator 32, was made in Germany during World War 11, using sodium catalyst and 0.78% vinyl chloride as a modifying agent ( 5 ) . It was employed as a October 1955
vulcanizable plasticizer and tackifier for synthetic rubber. Plastikator 32 was reported to have the consistency of strained honey. Very recently, Standard Oil Development Co. has announced ( I ) a new liquid polymer, C-Oil based on butadiene. No information has been released regarding its composition or the polymerization method used in its preparation. liquid polybutadiene i s highly unsaturated and dries oxidatively to form a protective film
The properties of a typical solvent-free sample of liquid polybutadiene are Molecular weight, approximately Viscosity, centipoises, 100' F. Color, Gardner Specific gravity, D ~ O Refractive index, nz2 Double bonds per Cd unit Iodine No.
1300 2500 10 0.91 1,519 0.8
325
There is considerable evidence that the liquid polymer made by the sodium-catalyzed reaction has a peculiar struct,ure unlike that of polybutadiene made by other polymerization processes. Butadiene polymers usually consist of long open chain molecules in which the butadiene units combine randomly by either 1,2- or 1,4-reaction.
-c-c-c-cC' C"
cI
- ~ - ~ ~ ~ -
c!I
1,2-Polymerization
1,4-Polymerization
In Butarez liquid polybutadiene, only about 80% of the expected double bonds are present, suggesting that considerable cyclization has occurred. This suggestion is supported by its specific refraction of 0.333, which is lower than that of open chain polyolefins of this carbon and hydrogen content but is in the range of compounds containing naphthene rings. Of the olefinic bonds
INDUSTRIAL AND ENGINEERING CHEMISTRY
209 1
PRODUCT AND PROCESS DEVELOPMENT Table 1.
Softener Parts/100 R b e r ExAdded tracted5
..
No softener
anhydride method (6) indicate the presence of conjugated Comunsaturation. It is to this Shore Freeze ounded peculiar structure, including HardPoint, kS-l1/2, nessa C. 212 F. cyclic structures, conjugated 69.8 29 59.2 unsaturation, and a high con62.5 29 37.8 tent of vinyl groups, that the 62.5 -38 31.2 e x c e p t i o n a l r e a c t i v i t y of - 39 64.0 sodium-catalyzed liquid poly-35 64.5 -34 .. butadiene is attributed. 51.8 -30 13.5 The liquid polymer has a -49 53.8 15.1 characteristic aromatic odor54.0 17.5 - 52 -41 53.5 17.0 probably that of low molecular weight polymer present in the reaction product. The odor is still detectable, though much less pronounced, in exhaustively stripped samples from which the most volatile components have been removed. The commercial product has a Gardner color of about 10. By the use of certain modifiers-e.g., dioxane-in the polymerization charge, much lighter colored products can be made. The modifier affects the course of the reaction, however, and the experimentally modified products that have been made to date have had less conjugated unsaturation and have had altered reactivity from that of the commercial polymer. Liquid polybutadiene is soluble in various organic solvents including hydrocarbons, diethyl ether, carbon disulfide, dioxane, pyridine, and butyl acetate. It is insoluble in water and has only limited solubility in acetone, the lower alcohols, Carbitol, and Cellosolve. The most interesting property of the liquid polymer is its ability to dry oxidatively to give protective films and to set t o a crossl i k e d resin a t elevated temperatures. Samples exposed to air a t room temperature form a surface skin within a few days, and brushed coatings containing a drier are hard-dry after about 8 hours a t room temperature. It is compatible with oleoresinous drying oils and provides an effective means of upgrading and improving their bodying and drying rates.
Effect of Various Softeners in Gasket Stock
..
Tensile Lb./Si Inch 3280 2560 2940 2320 1910 2920 1400 2760 2120
Elongation,
Swell,
305 370 330 355 270 375 315 225 415
46.8 56.8 33.8 34.4 29.5 40.1 75.5 21.7 19.0 17.2
%
%"
Liquid polybutadiene 10 2.0 10 9.0 TP-SOBO Diallyl sebacate 10 10.2 Flexol TOFd 10 10.2 10 9.7 Dibutyl phthalate Liquid polybutadiene 30 10.6 TP-9OB 30 21.6 Diallyl sebacate 30 24.9 Flexol TOF 30 27.4 O Seven days in 70/30 iso-octane/toluene a t 80' F. b Type A Durometer. C Polyether plasticizer from Thiokol Corp. d Trioctyl phosphate plasticizer from Carbide and Carbon Chemicals Corp.
..
..
that are present, approximately 60% are vinyl side chains arising from 1,a-addition of the butadiene. Both ultraviolet spectra, showing an absorption band a t a ,wave length of 238 millimicrons, and a determination of diene value by the Ellis-Jones maleic BAKING TIME
0 MINUTES
z
5 MINUTES
P
v)
x?
z 5
2 c z a Y
k!
14 MINUTES
-
Vulcanized liquid polybutadiene products may vary from viscous liquids to crumbly solids depending on compounding
Liquid polybutadiene can be vulcanized to yield products ranging in physical properties from viscous, tacky liquids to crumbly solids. A mixture of 5 parts sulfur and 2 parts butyl zimate in 100 parts liquid polymer cures to a soft solid in 3 hours a t 200' F. An alternate recipe employing 5 parts sulfur, 2 parts stearic acid, and 2 parts Tuads requires a vulcanization temperature of 270' to 300' F. Progressively harder products are obtained as the sulfur is increased to 10 or 15 parts. The solid prod-
30 MINUTES
2
4
6
8 IO 12 WAVELENGTH- MICRONS
Figure 1.
14
Infrared spectra
Table 11.
Properties of Cold Rubber Carcass Stocks Compounding Recipe
Parts 100 30 3.0 1.0 1.0
Rubber Philblack 0 Zinc oxide Stearic acid Agerite resin D Parts/lOO Rubber Softener Liquid P,BD Paraflux Liquid P B D Paraflux Liquid P B D Liquid P B D
10 10
Sulfur 2.5 2.5
A-32a 0.2 0.2
20 20 30 30
4.0 4.0 6.0 6.0
0.2 0.2 0.2 0.3
Santocureb 1.0 1.0 1.0 1.0 1.0 1.5
Tensile, Lb./Sq. Inch 3060 3080 2850 2500 2340 2300
Elongation,
%
495 520 476 450 400 340
AT,
F. 38.1 39.5 33.8 32.7 29.4 28.4
Min. to Blowout 9.4 10.9 14.3 20.8 30 30
Flex Life,
M
7.2 1.5 5.0 0.5 4.1 2.7
Oven Aged, 24 Hr., 212O F. Tensile, ElongaFlex lb./sq. tion, AT, life, % O F. M inch 2630 3 80 36.8 1.2 2520 390 36.5 0.4 2380 320 32.7 0.9 2090 360 33.1 0.2 2400 300 30.4 1.5 2030 250 28.8 1.2
e Reaction product of butyraldehyde and, butylidene aniline from Monsanto Chemical Co.
b N-Cyclohexyl-2-benzothiazolesulfenamide accelerator from Monsanto Chemical Co. 0
Saturated polymerized hydrocarbon plasticizer from C. P. Hall Co.
2092
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 47, No. 10
PRODUCT AND PROCESS DEVELOPMENT ucts exhibit very low tensile strength and poor abrasion resistance, but the partially vulcanized liquids have interesting adhesive properties. The latter are effective tackifiers in rubber stocks. The liquid polymer is an effective softener for natural or synthetic rubbers. It is a vulcaniaable softener-i.e., it covulcanizes with the rubber-and as a result is only partially extractable from the stock after vulcanization. This is shown in Table I which presents properties of a typical oil-resistant gasket stock based on Paracril A butadiene-acrylonitrile rubber. Liquid polybutadiene is an effective plasticizer (reduces compounded Mooney). Much less of it is extracted from the vulcanizate than the conventional nonvulcanizable softeners. Retention of the softener accounts in part for the higher swell of the polybutadiene-softened stocks. Their high freezing point is further evidence that the softener conbines chemically with the rubber during vulcanization. Liquid polybutadiene is also an effective softener in GR-S tread or carcass stocks in which it can be used satisfactorily in loadings as high as 30 parts per 100 rubber. Table I1 presents properties of a carcass stock based on 0 F (X-602) cold rubber. The most significant difference between the vulcanizates using liquid polybutadiene and those containing the conventional softener is the higher flex life of the liquid polybutadiene. In general, compounds having excellent properties are obtained with as much as 30 parts polybutadiene when high sulfur levels are employed. Drying Properties. When liquid polybutadiene is applied to a surface in a thin coat it will slowly polymerize to a hard film. The rate of polymerization or drying is faster than for drying oils such as tung or linseed. When the common metallic driers such as cobalt, manganese, and lead are added the drying rate is greatly increased, and satisfactory drying is obtained a t room temperature. The comparison of drying rates of 3-mil films of liquid polybutadiene and some of the drying oils is shown in Table 111. Infrared spectra were run 011 liquid polybutadiene and polybutadiene films baked a t 400' F. for 5, 14, and 30 minutes. The most significant change took place in the first 5 minutes of the baking. The spectra are shown in Figure 1. The change in absorption a t 3.22, 5.45, 6.07, 7.06, 10.08, and 11.00 microns between the baked and unbaked films indicates a marked change in vinyl olefin unsaturation. The decrease in absorption a t 10.37 microns shows the decrease in trans internal double bonds. The decrease in absorption a t 14.3and 14.7 microns indicates the disappearance of cis olefins. The increase in absorption a t 2.90 microns indicates the formation of hydroxyls and the increase in absorption a t 5.80 microns indicates the formation of carbonyls.
THIS LIQUID POLYMER
... is highly unsaturated
. . .thermosets to a hard, transparent coating . . . is vulcaaizable with sulfur and an accelerator
Possible uses are in protective coatings, as a casting and laminating resin, and as a vulcanizable rubber softener
The increased general absorption between 7.0 and 10.0 microns is characteristic of highly oxygenated polymers. The unbaked polybutadiene film absorbs strongly in the ultraviolet but after baking the absorption in this region disappears. Liquid polybutadiene polymerizes and increases in viscosity when heated. It copolymerizes with drying and semidrying oils to yield light-colored products with improved drying rates and harder films than the unmodified oils. The results of a typical experiment on heat bodying mixtures of oils and liquid polybutadiene are shown in Table IV. The liquid polymer is also compatible with a number of other types of commercial resins-e.g., petroleum and terpene polymers, Ester Gum C, rosin, and certain types of alkyds. It may be used as a grinding vehicle for pigments in both ball mill and
Table 111.
Drying Rates and Hardness Rub Dry
Tack Free
Hard Dry
Sward Hardness, Days 1 7 15
No Driers Polybutadiene Raw linseed Raw tung Safflower 22
46-48 hr. 2 . 5 days 5 days 7 days 4 days 6 days 3 days 4 days Driers, %-0.03
Polybutadiene Raw linseed Raw tung Safflower 22
6 48 36 36
2 hr. 36 hr. 24 hr. 24 hr.
4-5 days
12 32 Stili 'bft after 14 days Wrinkled
.... . ...
. ...
....
4
..
Co, 0.03 Mn, 0.15 P b
8 hr.
hr. hr. hr. hr.
20 26 Stili ';oft after 14 days Wrinkled 8
. . ..
..... .. ,
....
..
I I
i
BAKING T h E - I 5 MINUTES TOTAL/ TIME IN OVEN
-
1 I
l
i
Table IV.
Heat Bodying of Mixtures of Oils and Liquid Polybutadiene
I Linseed Oil
Soybean Oil
.. ..
90
io0 85 75
Liquid Bodying Time, PolyHr. a t 575: F. butadiene t o 2-2 Vis 10
15
85
25
75
..
..
15
25
Table
V.
Gardner Color 7
5
7
3%
1'/a 4'14 2 '/2
7 4 6+ 6+
to 1
Acid
No.
18.8 14.9 5.2
15.7 6.8 3.8
Moisture Vapor Transmission S ecifio Permeability, k O / S s . Cm./Mm. H d 24 Hr. a t 100' F. 3.9 1.4 1.7
Mg.
Formulation
TEMPERATURE, "f.
Figure 2. October 1955
Liquid polybutadiene Polybutadiene-linseed oil Hydroxylated polybutadiene-linseed oil Commercial phenolic varnish Commercial oleoresinous varnish
8.1 9.1
Polybutadiene film cure rates
INDUSTRIAL AND ENGINEERING CHEMISTRY
2093
PRODUCT AND PROCESS DEVELOPMENT Table VI.
a
Chemical Resistance
Chemical Ethyl alcohol Isoamyl acetate Methyl isobutyl ketone Iso-octane Benzyl ether Chloroform Toluene Sodium hydroxide, 5% Acetic acid Morpholine Tetrahvdrofurfurvl alcoho Cyclohexylamine Methylamine, 25% Propionaldehyde Carbitol Cellosolve Ethyl formate Methyl cyclohexano Pyridine Aniline Dioxane Chlorobenzene Carbon disulfide Ethylene chloride Dodecyl mercaptan Tests still in progress.
Time to Failure > 1 yeara
>
1 yeara
1 hour 4 months 4 months 1 month 10 days 16 days > 6 monthsa > 6 monthsa > 6 months
>
6 months
pressure cooker under 15 lb. per sq. inch gage steam pressure, and the coupons were subsequently examined for sulfide staining and loss of adhesion. It is apparent that the processing resistance of the experimental formulations increased with increasing zinc oxide content. All were superior to the commercial R enamel and those containing 3 or 4% zinc oxide were equal to or superior to the C enamel under the condition of the test. liquid polybutadiene forms castings with good electrical properties and heat stability
When liquid polybutadiene is heated at temperatures around 500" F. in the absence of air, it sets to a viscous gel and subsequently hardens to a highly cross-linked, transparent resin ( 4 ) . The castings have interesting electrical properties; for example, a t 106 cycles a dielectric constant of 2.42 and dissipation factor of less than 0.0005 are observed. They are also observed to have exceptional high temperature stability, undergoing little or no deterioration a t temperatures to BOOo F. Table VI11 shows typical properties of unfilled liquid polybutadiene castings prepared by curing a t different temperatures for various periods of time. The castings were prepared in test tubes immersed in a silicone oil bath for the indicated period of time. The resins show good adhesions to glass, and interesting results have been obtained in using them it as binders for the preparation of fiberglass-reinforced laminates. For example, an experimental 12-ply glass cloth laminate was found to have a flexural strength of 29,000 lb. per sq. inch, an Izod impact of 25.6 foot pounds per inch notch, and a resin-to-glass bonding strength of 1235 pounds per square inch.
roll mill operation. Because of its neutrality it can be used for acidic, basic, or inert pigments. Film Properties. A very interesting protective coating formulation is obtained by simply adding a drier to liquid polybutadiene, thinning with a mineral solvent to brushing viscosity, and applying to wood or metal surfaces. Two coats on wood produce a hard, tough finish that has high gloss but is flexible enough receive hammer blows without excessive cracking or turning white. Table VIII. Properties of Liquid Polybutadiene Casting Table V presents data showing moisture vapor transmission of films prepared from liquid polybutadiene formulations compared Curing Condition 6 Hr., 18 Hr., 6 Hr., 18 Hr., to commercial varnishes. The films were air dried on parchment 245O C. 245' C. 262O C. 262' C. Property paper and specific permeabilities measured by means of Payne 0.991 0.993 0.979 0,990 Density gram/oc. 84 88 87 cups. Shore D' hardness 73 0.280 0.350 0.218 0.89 Impact f t . lb Izod For harder, more chemically resistant films, baking in an oven 9050 8200 5400 Flex st;ength"lb./sq. inch 1315 4970 1270 5400 2800 Tensile lb./s' inch or under infrared lamps is required. The relationship between 4 1.3 3 18 Elongalion, * !$ baking temperature and pencil hardness of the film without drier 205 .... 91 64 Ht. dist. temp C. 0.3 4.97 1.30 Deformity undkr load, % is shown in Figure 2. When driers were added, the temperature required for 5-6 pencil hardness was reduced from 385" to 200" F. The chemical resistance of polybutadiene films applied to tinChemical modiflcations of liquid polybutadiene plate and baked 15 minutes at, 400° F. without driers is shown in yield products with interesting possibilities Table VI. The coated panels were immersed in the indicated Chlorination. Liquid polybutadiene is readily chlorinated by solvents at room temperature and examined periodically for film the introduction of gaseous chlorine to a 7% solution of the polyremoval, blistering, or other- evidences of failure. The characteristics of polybutadiene film-rapid drying a t conventional baking temTable VII. Dog Food Processing Tests peratures, freedom from odor and taste, and chemical resistProcessing Liquid Polybutadiene + Commercial Enamel PolyTime, Minutes butadiene 2% ZnO 3% ZnO 4% ZnO R C ance-suggest its use in food 6 6 6 6 4 4 Pencil hardnessa 0 can enamels, and the polymer 100 Adhesionb 100 100 100 100 100 has been evaluated for that use. Pencil hardness 5 6 6 6 2 3 60 0 0 0 0 1 Table VI1 shows results of food 1 Sulfide stainingo Adhesion 100 100 100 100 10 100 processing tests on tinplate 4 6 6 6 2 3 Pencil hardness 90 coupons having baked-on coat2 0 0 2 1 1 Sulfide staining 95 0 Adhesion 100 98 100 100 ings of liquid polybutadiene 4 5 5 6 1 3 Pencil hardness 120 alone and in admixture with 2 3 2 1 4 3 Sulfide staining Adhesion 5 100 100 100 0 95 various amounts of zinc oxide. 4 4 4 5 .. .. Commercial can enamels were Pencil hardness 150 4 4 4 1 .. .. Sulfide staining included as controls. The tests ' Adhesion 5 20 20 100 .. .. were made with dog food, 5 5 . . .. .. ..4 Pencil hardness 165 4 1 .. .. .. Sulfide staining which releases hydrogen sulfide 10 50 100 .. .. Adhesion during processing and provides a Hardness number of drawing pencil required to dent dried film. very severe conditions for can b Percentage of film not removed b y pressing on and removing Scotch tape. Arbitrary rating - 0 = no stain; 4 = very severe staining. enamels. Tests were run for various periods of time in a O
.
I
0
2094
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 47, No. 10
PRODUCT AND PROCESS DEVELOPMENT mer in carbon tetrachloride a t room temperatures. Hydrogen chloride is evolved during the reaction, but no difficulty from gelation is observed. Chlorinated products of 34 to 56 weight yo chlorine have been studied. The chlorinated products are light yellow, brittle solids that soften at about 200’ F. They are soluble in ketones, aromatic hydrocarbons, esters, and chlorinated solvents; insoluble in water, alcohols, and aliphatic acids. The solubility in organic solvents increases as the chlorine content of the polymer increases. The products resemble chlorinated rubber in many respects; however, they are of lower molecular weight and yield solutions of somewhat lower viscosity than that of chlorinated rubbers usually employed in paints. Hydroxylation. A solution of liquid polybutadiene reacts with hydrogen peroxide in the presence of organic acids t o yield hydroxylated liquid polybutadiene of variable hydroxyl content. -CHzCHCHzCH=CHCH2II
CH
+ 2Hz02
-+
-CH2CHCH&HOHCHOHCHz-
I
~ H Z
CHOH I
CH~OH Products having 21.5% oxygen have been made, but it has never been possible to approach complete reaction of the contained double bonds. The hydroxylated products can be separated into fractions on the basis of their solubility in acetone and n-pentane. As hydroxylation proceeds, the acetone-soluble fraction increases a t the expense of the pentane-soluble material. Products of more than about 20% oxygen content are completely soluble in acetone. The pentane-soluble material is a liquid much like the parent compound, but the more highly hydroxylated acetone-soluble fraction may vary from a viscous liquid to a rosinlike solid. Reaction with Maleic Anhydride. A mixture of liquid polybutadiene and maleic anhydride reacts vigorously at 270’ F. to yield a solid gel, insoluble in water, caustic, and organic solvents. The reaction is catalyzed by peroxides, and it may involve co-
New Epoxide Resins B y .
polymerization and cross linking as well as Diels-Alder addition of the maleic anhydride. The reaction may be moderated and controlled by the use of a solvent such as xylene. On heating a mixture of 10.1 grams liquid polybutadiene, 3.63 grams maleic anhydride, and 0.40 gram benzoyl peroxide in 40 grams xylene, a vigorous reaction began causing the xylene to reflux. Insoluble polybutadienemaleic anhydride copolymer soon separated from the solution. After 2 hours, about half the maleic anhydride had reacted. The highly cross-linked copolymer may be of interest for use in ion exchange resins. It reacts with sodium hydroxide solution, but the resulting sodium salt is not soluble in water. Acknowledgment
The authors gratefully acknowledge the contribution of W. B. Reynolds, who made many helpful suggestions in this work, and of their numerous associates who collaborated in the experimental program. They include J. F. Svetlik and H. E. Railsback who conducted rubber compounding studies; C. E. Wheelock who studied casting techniques; J. C. Hillyer, E. G. Marhofer, L. 0. Edmonds, and J. A. Delap who investigated vegetable oil upgrading and protective coatings; and V. L. Thornton, A. 0. Frenzel, and J. A. Favre who performed the infrared and ultraviolet absorption studies. literature cited
(1) Chem. Eng. News, 32, 2529 (1954). (2) Crouch, W.W. (to Phillips Petroleum Co.),U. S. Patent 2,631,175 (March 10, 1953). (3) Hillyer, J. C., and Wilson, J. F., Ibid., 2,550,695 (May 1, 1951). (4) Lee, M. M., private communication, 1954.
(5) Livingston, J. W.,Office Tech. Services Rept., PB-517 (1945). (6) McKinney, R.S., Halbrook, N. J., and Rose, G. W., Oil & Soap,
19, 141 (1943). (7) Schulze, W.A., and Crouch, W. W. (to Phillips Petroleum Co.) U. S. Patent 2,469,132 (May 3, 1949). (8) Schulze, W.A., Crouch, W. W., and Lynch, C . W., IND. ENG. CHEM.,41, 414 (1949). ACCEPTED May 2, 1955
RECEIVED for review January 14, 1955.
..
Reaction of Epichlorohydrin with Sulfonamides MERRILL COHEN Thornson Laboratory, General Electric Go., W e s t Lynn 3, Mars.
THE
reaction of bisphenols with epichlorohydrin to produce epoxide resins is of considerable commercial importance. The reaction of phenols with epichlorohydrin in alkaline solution yields phenyl glycidyl ethers as primary reaction products ( 2 , 7 , 16). CHa-CH-CH2C1 ArOH NaOH
+
‘d
-
+
ArOCH2-CH-CH2
\6
+ NaCl + HzO
(1)
The glycidyl ether may react with excess phenol to give a glycerol diether (g). NaOH ArOH -+ ArOCHz-CH-CH2
‘d
October 1955
+
Substitution of a dihydric phenol for the monohydric phenol in Reaction 1 yields the diglycidyl ether as one of the primary reaction products (26, 27). However, unless the reaction conditions are very carefully controlled, the reaction usually proceeds further to give polymeric epoxide-containing condensation products. HOArOH
NaOH
+ CHz-CH-CH2Cl
‘6
CH~-CH-CHZ-
‘d
[OA~OCH~CHOHCHZ]
ArOCH2CHOHCHZOAr (2)
INDUSTRIAL AND ENGINEERING CHEMISTRY
-0ArOCH2-CH-CH2
\/
(3)
0
2095
