25  US 6,291,723 Bl  26  TABLE 40A-45A  TABLE 40B-45B  EXAMPLE 47  EXAMPLE 42A  EXAMPLE 40A  EXAMPLE 46  The procedure of Example 31 was followed but using 8.8  moles of phenol and a mole ratio of 0.5 of the diene to the  phenol and a diene addition time of 3.25 hours while  In a manner similar to Example 42, but by replacing  phenol with an equimolar amount of meta-cresol, approxi- In a manner similar to Example 40 but replacing phenol  by 50% of the equimolar amount of resorcinol, using twice  the weight of resorcinol by 1:1, by weight, ortho-xylene/  ortho-cresol as solvent, neutralizing catalyst, removing sol› vent and any unreacted resorcinol, a product can be obtained  which has approximately equal amounts of aryloxy and  hydroxyaryl groups.  In a manner similar to Example 40 above other non› conjugated dienes and phenols can be used in place of the  diene and phenol used in Example 40. Also, mixtures of  reactant monomers, including conjugated dienes, can be  used such as: 10 mole % of diene can be replaced by  2,5-dimethyl-2,4-hexadiene, a conjugated diene; 20 mole %  of phenol can be replaced by m-cresol; and 10% of phenol  can be replaced by resorcinol. However, with resorcinol  which is a solid (melting point of about 111 °  C.) one would  need to use an inert solvent such as toluene, xylene,  chlorobenzene, or a lower reactive, removable phenolic such  as ortho cresol to at least partially dissolve the very reactive  resorcinol and the reaction conditions would be relatively  mild, e.g., temperatures of about 60°  C., at least initially.  A  one liter multi-neck flask to be fitted with overhead  stirrer, thermometer, condenser, and addition funnel was  charged with: 580 g, phenol (6.16moles containing 0.04%  water); 0.48 gm triflic acid; and 1.44 g .!’-l_-methyl pyrrolidone  and heated under nitrogen to 100°  C.  A  solution of 94.0 g of  d-limonene  (HP,  0.69 mole) and 91.2 g of dicyclopentadiene  (Ultrene 99, 0.69 mole) was then added over 2 hours to the  phenol plus the catalyst system which was at 100°  C.–1 °  C.  . The reaction solution was further heated at 100°  C. for 2  hours whereupon catalyst was neutralized with 0.85 g of  15% sodium hydroxide in water. Phenol was then removed  by vacuum distillation as in Example 31 followed by steam  sparging with 150 ml water at 155-160°  C. under 20 inches  of vacuum. Product was dried at 160°  C. under 30 inches of  vacuum . Yield of dark amber gum was 295 g and vacuum  distillate was 437 g. Product was characterized as follows:  phenol of less than 0.05%; Mw/Mn=237/200 (204/159  including SEC peak at 95–1); viscosity, 250 cps (100°  C.)  and 1500 cps (70°  c.).  Dicyclopentadiene/d-Limonene/ Phenol Condensate  (c) Does not contain an SEC peak at 95 – 1.  (ct)values in parentheses include the phenoxy-dicyclopentadiene compound  and a trace of phenol.  (c)Based on % of phenol and diene, by weight charged to the reaction.  One gram (g) of the dicyclopentadiene/phenol resin of  Example 45 above was exhaustively extracted with 5.0 g of  n-heptane, evaporated and vacuum dried to give 0.34 g  (34%) of a tacky resin. In contrast product from Example 50  is essentially insoluble in heptane.  The following shows the procedure and results for the  isolation of phenol-dicyclopentadiene product. One hundred  g of product equivalent to that of Example 40 was dissolved  in 150 ml of n-hexane and extracted with a solution of 100  ml methanol and 30 ml of water. The methanol-water phase  was evaporated and vacuum dried at 60°  C. to give 2.9 g of  dark amber, viscous liquid. Hexane was removed to give 95  g of amber syrup which after cooling was extracted with 200  g of ice cold 10% sodium hydroxide in water. The aqueous  extract was washed with 50 ml of n-heptane and then  precipitated by gradual addition to stirred ice cold 50 g  concentrated HCL. The precipitated oil was extracted with  70 ml of n-hexane and this solution was washed with 50 ml  water. Hexane was evaporated and residue dried at 60--100°  C. at 28.5 to 29 inches of vacuum for 3 hours. Yield of amber  syrup was 30 g and was characterized as follows: % OH of  7% (theory is 7.5%) Mw/Mn of 176/143 (includes SEC peak  at 96) and it was noticed that only one significant peak was  present at 132 whereas the theoretical for the phenol- dicyclopentadiene compound is 226; viscosity of 20,600 cps  (25° C.) wherein 66.8% by weight of this syrup is the  phenol-dicyclopentadiene compound; 11.4% is the  phenoxy-dicyclopentadiene compound (SEC peak at 96);  and 21.8% is that of higher molecular weight compounds  (SEC peak at 233).  mately equal amounts of aryloxy-dicyclopentadiene com› pound and hydroxyaryl-dicyclopentadiene compound can be  obtained.  (,)After 2 hour diene feed at 60°  C. and 2 hour hold at 60°  C.  (b)Refractive Index (Refr. Ind.) (24.5-26.5°  C.) and viscosity (vise) (25°  C.) of reaction solution.  (ct)Mw/Mn - 270/186 (160/118)  (c)Mw/Mn - 333/209 (219/130)  (f)Two hours at 60°  C. after diene addition, the dicyclopentadiene content  was 1.73% which represents 95.5% conversion.  For (ct) and (c) above, the values in parentheses include the SEC peak at 95  – 1.  Reaction Conditions of Post Feed Tem12eratures and Time Study  Time  Temperature  Solution(b)  EX  (hours)<’)  (°c.)(,)  Refr. Ind.  Vise.  40  2 and  V,  90  1.5620  67.6  41  3 and V4  90  1.5619  68.6  42  1 and V6  80  1 and  V2  100  1.5636  43(f)  2  60  2.25  100  1.5652  111  44  2  14o<ctJ  2  16o(c)  672  5  180  29,500  45  4  115-160  268  3  170  5160  Condensate Properties  Viscosity,  Ex  Yield, %(c)  Refr. Ind.  cps (25° c.)  Mw/Mn(ct)  40  62  1.5714  767  157/146 - 41  61  1.5717  908  156/146 - 42  56  1.5751  2580  170/150 (143/122)  43  1.5767  4,480  175/152 (149/125)  44  61  Solid  520 (125°  C.)  642/286 (c)  45  64  Solid  156 (125°  C.)  473/241 (c) 