29  US 6,291,723 Bl  30  COMPARATIVE EXAMPLE 51  COMPARTIVE EXAMPLE  52  COMPARATIVE EXAMPLE 50  EXAMPLE 53  Example 48 was followed using 9. 9 moles phenol (instead  of 8.8) and 3.0 moles of the diene but after the one hour at  Dicyclopentadiene/Phenol Condensate at Mole  Ratio of 0.30  Example 1 of U.S. Pat. No. 4,927,905 was essentially  followed but at a mole ratio of 0.077 of dicyclopentadiene  to phenol. Thus, dicyclopentadiene (132 g., 1.0 mole) was  added over one hour under nitrogen blanket to a solution of  phenol (1,223.3 g ,13 moles) and boron trifluoride etherate  ( 6.8 g, 0.5% on phenol) at 70°  C. The reaction was then  heated over 4 hours to 150° C. and maintained at this  temperature for 1.5 hours. Reaction was then cooled to 60°  C. and catalyst neutralized with 6.5 g of 45%  KOH.  Phenol  was recovered by vacuum distillation to 190°  C. at 26 inches  Preparation of Dicycloperitadiene/Phenol Resin  Using Boron Trifluoride Catalyst and at a Mole  Ratio of 0.077 of Dicyclopentadiene to Phenol  From the above Comparative Example 52 and Table 52 it  can be seen that the very strong methanesulfonic acid (about  0.5 times the acidity of sulfuric acid and about twice the  strength of  HCI  measured by conductivity in acetic acid at  25°  C.) is relatively ineffective in comparison to triflic acid.  After 11 hours at 90°  C., as shown in Table 52 above, the  reaction mixture was neutralized and then analyzed. The  analysis showed: 14.9% of unreacted dicyclopentadiene  which translates to but a 61 % conversion of the diene; and  a ratio of about 3.4 of phenoxy-dicyclopentadiene com- pound to hydroxyphenyl-dicyclopentadiene compound.  The calculation for hydroxyl equivalent is:  (B-A)(IN)(0.017)(100) divided by Sample Weight, in grams.  17x100 divided by %OH.  A  determination of the hydroxyl number (and equivalent)  is made as follows:  A  solution of 2.0 g sample is refluxed for  2 hours with 25 ml of pyridine/acetic anhydride solution  (from 250 ml pyridine plus 60 ml of the anhydride). The  reflux condenser is rinsed with 5 ml water and the contents  heated for an additional 5 minutes. Heat is removed and the  condenser rinsed with 25 ml methanol. After cooling to  room temperature, the contents are titrated with 1.0 N  sodium hydroxide to pH of 9 by using the pH meter. The titre  is expressed as "A". For the blank ("B"), a mixture of the  same volume of acetic anhydride, pyridine and water as used  above is mixed and allowed to stand for 15 minutes shortly  before titration, the same amount of methanol as was used  above as a rinse is added. "B" is expressed in mls  (milliliters). The calculation for "%OH" is:  The procedure of Example 38A was followed except that  an equimolar amount of methanesulfonic acid(l.3:3g of  10% acid in phenol) replaced 2.08 g of 10% triflic acid in  phenol. Essentially, no reaction occurred after one hour at  45°  C. after diene addition at 45°  C. (refractive index of  1.5314 at 27.7° C.). Very little reaction occurred after  another 4 hours at 70°  C. when the refractive index was  1.5344 (27.6°  C.). This is versus a refractive index of 1.5548  (26.1 °  C.) for Example 38A at this time and 1.5569 after 7  hours at 70°  C. The reaction was then heated to 90°  C.  wherein the refractive index changed as shown in Table 52  below wherein R. I. is refractive index at 25–0.5°  C.  Dicyclopentadiene/Phenol Condensate Using  Methanesulfonic Acid Catalyst and Acetanilide  Retarder  (’ffhe calculated % of OH: for the bis(hydroxyaryl)-non-conjugated diene  is  10.6; for the aryloxy-non-conjugated-diene compound is 0.0 and  hydroxyaryl-non-conjugated-diene compounds is  7.5; and for the polycon- densate is  7.5. The polycondensate is a chain of self polymerized units  and polymerized mixture of units.  (b)Contains traces of methanol and hydroxyphenyl-dicyclopentadiene com› pound.  Dicyclopentadiene (198.5 g, 1.5 moles) was added over  one hour under nitrogen blanket to a solution of phenol (565  g, 6.0 moles) and boron trifluoride etherate (2.25 g, 0.4% on  phenol) at 70°  C. Reaction mixture was further heated and  phenol and product recovered as in Example 50. Product  (317 g) was characterized as follows: viscosity of 20,900 cps  at 125°  C.; 942 cps at 150°  C.; Mw/Mn of 580/318; and  phenol-dicyclopentadiene compound of about 3%.  Comparative Example for Preparation of  Dicyclopentadiene/Phenol Resin Using Boron  Trifluoride Catalyst and Mole Ratio of 0.25 of  Dicyclopentadiene to Phenol  of vacuum and then the residue steam sparged with 100 ml  water at 185-190°  C. under 26 inches of vacuum. Product  (312 g) was characterized as follows: viscosity of 1210 cps  at 125°  C. Mw/Mn 322/262; phenol of <0.05%; boron of  0.027%; fluorine of 1.06%; phenol-dicyclopentadiene com› pound of trace ( <1 %). Also no phenoxy-dicyclopentadiene  compound (ether) was detected.  TABLED  TABLE 52  Properties of Condensates Obtained by  Size Exclusion Chromatography (SEC)  % OH(,) and  1:1 Ether,  1:1  III/IV  (hydroxyl  (EX)  %  Phenolic, %  Ratio  equivalent)  Viscosity  A(b)  B  C  D  E  40  38A  42  43  33  47  36  45  44  31  F  97.5  59.2  3.6  82.9  19.7  54.1  60.5  41.6  38.2  33.0  0.4  0  68.7  0  2.5  17.2  58.6  15.8  72.2  37.9  33.0  42.2  43.5  40.5  24.5  16.3  31.3  0  39  3.44  0.06  5.2  0.27  1.4  1.83  0.99  0.88  0.81  0.02  0  2.19  0.5(3,400)  m.p. 65-67°  C.  2.01(845)  7.26(234)  2.21(770)  767  431  2580  2.57(662)  4480  2.93(579)  12300  108,200  383  156(125°  c.)  7.39(230)  520(125°  c.)  270  10.5  Solid at 25°  C.  Hours at 90°  C.  3  5  7  9  11  RI. (25 – 0.5°  C.)  1.5370  1.5404  1.5430  1.5449  1.5473  1.5497 