PHENOLIC HYDROXYL-CONTAINING COMPOSITIONS AND EPOXY RESINS PREPARED THEREFROM AND SOLID COMPOSITIONS PREPARED THEREFROM

Abstract: This invention is directed to phenolic hydroxyl-containing compositions and to epoxy resins prepared therefrom, the compositions having more than one phenolic hydroxyl group and more than one aromatic ring per molecule, which is substantially free of ether groups, and which composition results from an acid catalyzed reaction of (A) at least one aromatic compound containing at least one aromatic hydroxyl group and from one to two aromatic rings and at least one ortho or para position relative to a hydroxyl group available for ring alkylation; with (B) at least one unsaturated hydrocarbon. The invention is characterized in that component (B) is selected from (1) monounsaturated or diunsaturated hydrocarbons having from 4 to 6 carbon atoms or mixtures thereof; (2) unsaturated hydrocarbons containing an average of from 6 to 55 carbon atoms per molecule and containing not more than 94 weight percent dicyclopentadiene, (3) oligomers and/or cooligomers of hydrocarbon dienes, which dienes have from 4 to 18 carbon atoms, and which dienes contain at least 6 percent by weight of diene other than dicyclopentadiene; and (4) mixtures thereof. This invention is also directed to an epoxy resin composition resulting from the dehydrohalogenation of the reaction product of an epoxy alkyl halide with the composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule as described above. The epoxy resins of this invention have improved mold shrink properties and improved aqueous solvent resistance.

Description: PHENOLIC HYDROXYL-CONTAINING COMPOSITIONS AND EPOXY RESINS PREPARED THEREFROM AND SOLID COMPOSITIONS PREPARED THEREFROM The present invention concerns phenolic hydroxyl-containing compositions, epoxy resins prepared therefrom and solid compositions prepared therefrom. Epoxy resins have heretofore been prepared from condensates of aromatic hydroxyl-containing compounds and aldehydes and ketones. Commercially available high performance epoxy resins such as the phenol-formaldehyde resins possess excellent properties but in some instances may have less than desired moisture or chemical resistance properties, electrical properties or low elongation values. Glycidyl ethers of polyhydric phenols derived from monohydric phenols and dicyclopenta¬ diene are described in U.S. Patent No. 3,536,734. In addition to overcoming one or more of the aforementioned deficiencies, the epoxy resins of the present invention, in some instances, have improved mold shrink properties and improved aqueous solvent resistance. __ OMPI One aspect of the present invention pertains to a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule, which is substantially free of ether groups and which composition results from an acid catalyzed reaction of (A) at least one aromatic compound containing at least one aromatic hydroxyl-group and from one to two aromatic rings and at least one ortho or para position relative to a hydroxyl group available for ring alkylation; with (B) at least one unsaturated hydrocarbon, wherein components (A) and (B) are employed in quanti¬ ties which provide a mole ratio of component (A) to component (B) of from 1.8:1 to 30:1, preferably from 1.8:1 to 20:1 and wherein said acid catalyst is employed in a quantity of from 0.01 percent to 5 percent, preferably from 0.3 percent to 1 percent by weight based upon the weight of component (A) characterized in that component (B) is selected from (1) monounsaturated or diunsaturated hydrocarbons having from 4 to 6 carbon atoms or mixture thereof; (2) unsaturated hydrocarbons containing an average of from 6 to * 55 carbon. atoms per molecule and containing not more than 94 weight percent dicyclopentadiene; (3) oligomers and/or cooligomers of hydrocarbon dienes, which dienes have from 4 to 18 carbon atoms and which dienes contain at least 6 percent by weight of dienes other than dicyclopentadiene; and (4) mixtures thereof. Preferably component (B) is a composition comprising from 20 to 94 percent by weight of dicyclo- pentadiene, from 1 to 30 percent by weight of dimers other than dicyclopentadiene and codimers of C 4 -C 6 hydrocarbons, from zero to 10 percent by weight of oligomers of C 4 -C 5 dienes; and the balance, if any, to provide 100 percent by weight of C 4 -C 8 alkanes, alkenes and dienes. Another aspect of the present invention concerns an epoxy resin composition resulting from the dehydrohalogenation of the reaction product of (C) an epoxy alkyl halide with (D) a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule, wherein components (C) and (D) are employed in quantities which provide a ratio of epoxy groups to phenolic hydroxyl groups of from 1.5:1 to 20:1, preferably from 3:1 to 5:1, and characterized in that component (D) is the composition described above. Another aspect of the present invention are solid compositions resulting from reacting in the presence of an effective quantity of a suitable catalyst, (I) at least one epoxy resin having an average of more than one 1,2-epoxy group per molecule with (II) at least one material having an average of more than one phenolic hydroxyl group per molecules characterized in that component (II) is the phenolic hydroxyl-containing composition described above, or that component (I) is the epoxy resin composition described above, or that OMP both components (I) and (II) are the compositions described above. Suitable aromatic hydroxyl-containing compounds which can be employed herein include any such compounds which contain one or two aromatic rings, at least one phenolic hydroxyl group and at least one ortho or para ring position with respect to a hydroxyl group available for alkylation. Particularly suitable aromatic hydroxyl- containing compounds which can be employed herein include , for example, phenol, chlorophenol, bromo- phenol, methylphenol, hydroquinone, catechol, resorcinol, guaiacol, pyrogallol, phloroglucinol, isopropylphenol, ethylphenol, propylphenol, t-butylphenol, isobutylphenol, octylphenol, nonylphenol, cumylphenol, p-phenylphenol, o-phenylphenol, m-phenylphenol, bisphenol A, dihydroxy- diphenyl sulfone, and mixtures thereof. Particularly suitable unsaturated hydrocarbons which can be employed herein include, for example, a dicyclopentadiene concentrate containing from 70 to 94 percent by weight of dicyclopentadiene; from 6 to 30 percent by weight of dimers other than dicylopentadiene and codimers of C 4 -C 8 hydrocarbons such as, for example, cyclopentadiene-isoprene, cyclopentadiene-piperylene, cyclopentadiene-methyl cyclopentadiene, and/or dimers of isoprene, piperylene, and methyl cyclopentadiene; from zero to 7 percent by weight of oligomers of C.-Cg dienes such as, for example, C 14 -C ιa trimers; and the balance, if any, to provide 100 percent by weight of C 4~ C 5 alkanes, alkenes and dienes such as, for example, butadiene, isoprene, piperylene, cyclopentadiene, OMPI cyclopentene, 2-methylbutene-2, cyclohexene, cyclo- hexadiene, methyl cyclopentadiene, and 1,5-hexadiene. Methods of preparation for these dicyclopentadiene concentrates and more detailed descriptions thereof can be found collectively in U.S. Patent No. 3,557,239 issued to Gebhart et al. and U.S. Patent No. 4,167,542 issued to Nelson. Also, particularly suitable unsaturated hydrocarbons which can be employed herein include a crude dicyclopentadiene stream containing from 20 to 70 percent by weight of dicyclopentadiene; from 1 to 10 percent by weight of dimers other than dicyclopentadiene and codimers of C 4 -C 8 hydrocarbons (described above), from zero to 10 percent by weight of oligomers of C 4 -C 8 dienes, and the balance to provide 100 percent, C 4 ~C g alkanes, alkenes and dienes. Also, particularly suitable unsaturated hydrocarbons which can be employed herein include a crude piperylene or isoprene stream containing from 30 to 70 percent by weight of piperylene or isoprene, from zero to ten percent by weight C 8 -C 12 dimers and codimers of C 4 -C 8 dienes, and the balance to provide 100 percent by weight of C 4 -C 8 alkanes, alkenes and dienes. Also, particularly suitable are hydrocarbon oligomers prepared by polymerization of the reactive components in the above hydrocarbon streams e.g., dicyclopentadiene concentrate, crude dicyclopentadiene, crude piperylene or isoprene, individually or in combi¬ nation with one another on in combination with high purity diene streams. OMP Examples of such hydrocarbon compositions include, for example, an unsaturated hydrocarbon compo¬ sition comprising from 90 to 100 percent by weight of the di er of piperylene, from 0 to 10 percent by weight of higher molecular weight oligomers of piperylene, and from 0 to 4 percent by weight of piperylene; and an unsaturated hydrocarbon prepared by the oligomerization of dicyclopentadiene concentrate, which oligomerization product contains an average of from 12 to 55 carbon atoms per molecule. Suitable acid catalysts which can be employed herein include, for example, Lewis Acids, alkyl, aryl and aralkyl sulfonic acids and disulfonic acids of diphenyloxide and alkylated diphenyloxide, sulfuric acid, and mixtures thereof. Particularly suitable are such Lewis Acids as BF 3 gas, organic complexes of boron trifluoride such as those complexes formed with phenol, cresol, ethanol, and acetic acid. Also suitable Lewis acids include aluminum chloride, zinc chloride, and stannic chloride. Also suitable catalysts include, for example, activated clays, silica, and silica-alumina complexes. Suitable epoxy alkyl halides which can be employed herein include those represented by the formula R R H X-C-C-C-H wherein each R is independently hydrogen or R 0 an alkyl group having from 1 to 6 carbon atoms and X is a halogen. Particularly suitable epoxy alkyl halides include, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, methylepichlorohydrin, methylepibromo- hydrin, methylepiiodohydrin, and mixtures thereof. The epoxy resins of the present invention can be cured by themselves or in mixtures with other epoxy resins with well-known curing agents or with the reaction products of the phenols and unsaturated hydrocarbons described herein or mixtures of them with the well known curing agents. Suitable epoxy resins which can be employed to produce solid compositions, include, for example, those glycidyl ethers of aliphatic and aromatic compounds having an average of more than one glycidyl ether group per molecule. Those epoxy resins include the glycidyl ethers of neopentyl glycols, dibromoneopentyl glycol, polyoxypropylene glycol, resorcinol, catechol, hydro- quinone, bisphenol A, phenol-formaldehyde condensation products, tetrabromobisphenol A and mixtures thereof. Suitable phenolic hydroxyl-containing materials which can be employed to produce solid compositions include, for example, resorcinol, catechol, hydroquinone, bisphenol A, tetrabromobisphenol A, phenol-formaldehyde condensation products, phenolic terminated reaction products of epoxy resins having an average of more than one glycidyl ether group per molecule and a phenolic hydroxyl-containing compound having an average of more than one phenolic hydroxyl group per molecule, and mixtures thereof. Suitable epoxy resins, phenolic hydroxyl- -containing materials and curing agents, are more fully described in HANDBOOK OF EPOXY RESINS by Lee and Neville, McGraw-Hill, 1967 and U.S. Patent Nos. 3,477,990; 3,949,855 and 3,931,109. Suitable catalysts which can be employed in the reaction of 1,2-epoxy-containing materials with phenolic hydroxyl-containing materials include, for example, alkali metal hydroxides, and phosphonium and ammonium compounds such as those mentioned in the above reference handbook and U.S. Patent Nos. 3,477,990; 3,948,855 and 3,931,109. Particularly suitable curing agents include, for example, primary, secondary and tertiary amines, polycarboxylic acids and anhydrides thereof, polyhydroxy aromatic compounds, and combinations thereof. In preparing the compositions of the present invention containing an average of more than one phenolic hydroxyl group and more than one aromatic ring per molecule, the reaction between the phenolic hydroxyl- -containing compounds and the unsaturated hydrocarbons can be conducted at temperatures of from 33°C to 270°C, preferably from 33°C to 210°C. The following examples are illustrative of the present invention, but are not to be construed as to limiting the scope thereof in any manner. Oligomer Prep A To a Parr reactor, equipped with a stirrer, heater, temperature and pressure indicators was charged OMPI - ~ 1600 gms of dicyclopentadiene (DCPD) concentrate. (DCPD concentrate contains between 80 and 85 percent DCPD, between 13 and 19 percent codimers of cyclopenta¬ diene with other C 4 -C 8 dienes and between 1.0 and 5 percent lights (C 4 -C 8 mono-olefins and di-olefins). The reactor was pressured to 200 psig (1480 kPa) with nitrogen gas and heated to 185°C for 2 hours and 20 minutes (8400 s). Maximum observed gauge pressure was 272 psi (1977 kPa). The heat was turned off, the reactor vented and the contents, a white slurry at room temperature, were removed. The product was believed to be a mixture of C 4 -C 8 dimers, trimers, tetramers and pentamers having an average molecular weight of 198. Oligomer Prep B To a Parr reactor equipped as in Oligomer Prep B was added 1600 gms of a similar concentrate of dycyclopentadiene. The reactor was pressurized to 200 psig (1480 kPa) and heated to 200°C, and held at that temperature for 2 hours (7200 s). The resultant product was a waxy solid at room temperature and believed to be a mixture consisting primarily of C 4 -C 8 trimers, tetramers, pentamers and hexamers having an average molecular weight of 264. ■Example 1 — (Phenolic Resin Prep) To a reactor, equipped with a stirrer, conden¬ ser, thermowell and heater, were added 846.9 gms (9.0 moles) of phenol, 50 gms of water and 5.0 gms (0.6 percent based on phenol) of concentrated sulfuric acid. The contents of the reactor were heated to 124°C. 1.5 moles of hydrocarbon oligomer, prepared in a manner similar to Oligomer Prep A, but with a molecular weight of 214, was added to the reactor over a 1-hour (3600 s) OMPI period. 50 Grams of toluene was used to wash oligomer particles from the dropping funnel. After 1 hour 10 minutes (4200 s), the reactor temperature was set at 190°C and the vacuum distilling assembly put in place. Distillation was conducted over a 3-hour (10800 s) period, finishing at 210°C and 1 mm of mercury (0.1 kPa). The total distillate was 663.1 gms, providing a recovered product of 611.4 gms. Table I describes further results of this synthesis. Example 2 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 were added 2258 gms (24 moles) of phenol and 30.8 gms of BF 3 etherate in 40 gms of carbon tetrachloride. The reactor was heated to 73°C. Over a two hour and 51 minute (10260 s) period, with temperatures between 73°C and 83°C, was added 824 gms (4 moles) of an oligomer bearing the commercial designation of RI-300. RI-300, which is available from CXI Incorporated, is an oligomer believed to have been prepared from mainly piperylene with lesser amounts of cyclopentadiene, isoprene, butadiene and methyl cyclopentadiene. The estimated mole weight is 206. After the oligomer addition was complete, the temperature was increased to 150°C over 3 hours and 20 minutes (12000 s). A reaction time of 6 hours and 25 minutes (23100 s) was allowed at 150°C, at which time distillation was started. The total distil¬ late was 1830.4 gms and the yield was 1322.4 gms. See Table I for further results of this synthesis. Example 3 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 was added 1693.8 gms (18 moles) of molten phenol and 10.3 gms BF 3 etherate in 10 gms of carbon tetrachloride. The mass was heated to 70°C at which point slow addition of 599.4 gms of dicyclopentadiene concentrate was begun. (The DCPD concentrate contained 83 percent DCPD and 0.9 percent lights - the remainder being primarily mixed C 4 -C 8 dienes.). After 1/2 of the dicyclopenta¬ diene concentrate had been added, another 10.3 gms of BF etherate in 10 gms of carbon tetrachloride was added to the reactor. The total hydrocarbon addition time was two hours (7200 s) within a temperature range of 70°C to 80°C. The reaction mass was heated to 155°C over a 5 hour and 39 minute (20340 s) time period. The reaction was held to 155°C for 7 hours and 41 minutes (27660 s) at which time distillation was begun. The reaction was completed at 165°C and 1 mm of mercury (0.1 kPa). The total distillate was 995 gms providing a yield of 1338.8 gms. See Table I for additional results of this synthesis. Example 4 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 were added 1974 gms (21 moles) of molten phenol and 23.2 gms of BF 3 e'therate in 60 gms of carbon tetrachloride. At a temperature of 65°C the addition of 924 gms (3.5 moles) of a hydrocarbon oligomer prepared in a manner similar to Oligomer Prep B was begun. 30 Grams of toluene and 30 gms of carbon tetrachloride were added to the oligomer as a washing solvent. The oligomer addition time was 5 hours and 8 minutes (18480 s) within a temperature range of 65°C to 84°C. When addition was complete, the reaction was heated to 160°C over a 6 hour and 41 minute 24060 s) period. After 5 hours (18000 s) at that temperature vacuum distillation was started. The reaction was finished at 200°C and 1 mm of mercury (0.1 kPa). Total distillate recovery was 1284 gms to provide a total yield of 1757.2 gms. See Table 1 for additional results of this synthesis. Example 5 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 were charged 1599.7 gms (17 moles) of phenol and 9.0 gms of BF 3 etherate, 0.4 percent by weight based on total expected charge. The BF 3 etherate was mixed with 10 gms of carbon tetrachloride prior to addition. The catalyst and phenol were heated to 75°C and slow addi- tion of 647 gms (4.857 moles of 99.1 percent C-, Q reac- tives) dicyclopentadiene concentrate begun. The total addition time was 2 hours and 43 minutes (9780 s) within a temperature range of 75°C-85°C. When the hydrocarbon addition was complete, the temperature was gradually raised to 150°C over a period of 4 hours (14400 s). The reaction was conducted for an additional 1 hour and 30 minutes (5400 s) before starting vacuum distillation. The reaction was finished at 250°C and 1 mm of mercury (0.1 kPa). Total distillate was 875 gms for a yield of 1390.7 gms. See Table I for additional results of this synthesis. Example 6 — (Phenolic Resin Prep) Using the same molar ratios of phenol and hydrocarbon as in Example 5, the BF 3 etherate catalyst was reduced from 0.4 percent by total weight to 0.1 percent by total reactant weight. Heat cycles were approximently the same. Table I describes the results of this synthesis. Example 7 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 were added 880.8 gms (8.0 moles) of resorcinol and 4.6 gms OMPI BF 3 etherate in 5 gms of carbon tetrachloride. The contents were heated to 110°C and 264 gms (2.0 moles) of dicyclopentadiene concentrate were added over a 1 hour and 25 minute (5100 s) time period. The reactor temperature was controlled between 110°C and 112°C. When dicyclopentadiene addition was complete, the reactor was gradually heated to 160°C over a 4 hour (14400 s) time period. After an additional 1 hour (3600 s), the temperature was reduced and some water added. The water, which did not separate, and 350 gms of resorcinol were removed by vacuum distillation. The resultant product was predominantly a mixture of tetra- functional and hexafunctional derivatives of resorcinol and Cg-C-,, dienes. Additional results of this synthesis are described in Table I. Example 8 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 were added 2162 gms (20 moles) of ortho-cresol and 12.9 gms of BF 3 etherate in 20 grams of carbon tetrachloride. The mass was heated to 68°C. 1057 Grams (8.0 moles) of a 99.9 percent reactive diene hydrocarbon stream contain¬ ing 85 percent dicyclopentadiene were added over the next 4 hours and 8 minutes (14880 s). The reaction temperature during this time was maintained between 68°C and 85°C. The reactor was slowly heated to 150°C over 6 hours 21600 s). The product was then vacuum distilled and 1111 gms of ortho-cresol recovered. The resultant product was primarily the result of 2 moles of ortho-cresol reacting with 1 mole of diene hydrocarbon. Additional results are described in Table I. Example 9 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 were added 3387.6 gms (36 moles) of molten phenol and 17.9 gms of BF 3 etherate in 10 gms of carbon tetrachloride. The reactor was heated to 70°C and 1081.1 gms (8.18 moles) of 99.9 percent reactive dicyclopentadiene concentrate employed in Example 8 was added over a 3 hour and 14 minute (11640 s) period. The temperature during this addition period was maintained between 70°C and 85°C. After the hydrocarbon addition was complete, the mass was heated to 145°C over a 4 hour (14400 s) time period. An additional reaction time of 3 hours (10800 s) was givin at that temperature and vacuum stripping of unreacted phenol commenced. The reaction was finished at 223°C and 1 mm of mercury (0.1 kPa). . Total distil¬ late was 2160 gms providing a product yield of 2326.6 gms. See Table I for additional results of this synthesis. Example 10 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 were added 1854 gms (9 moles) of p-octyl phenol (diisobutyl phenol) and 11.6 gms BF 3 etherate in 20 gms of carbon tetrachloride. The temperature was set at 80°C and 475.7 gms of 99.9 percent active DCPD concentrate were added over a 1 hour and 46 minute (6360 s) period. The reactor was heated from 90°C to 165°C over an 8 hour (28800 s) time period and vacuum distillation begun. 85 Grams of unreacted hydrocarbon and 915 grams of octyl phenol were removed. The resultant product contained mainly 2 and 3 phenolic hydroxyls per molecule. See Table I for further results of the synthesis. Example 11 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 were added 1035.1 gms (11 moles) of phenol and 9.5 gms of BF 3 etherate in 200 gms of toluene. The temperature was set at 40°C. A crude hydrocarbon stream containing mainly alkanes, alkenes and dienes in the C 5 to C 1Q range, 355.5 gms (estimated at 3.33 moles of active product) was added over a 7 hour and 3 minute (25380 s) time period. A summary analysis of this stream is as follows: n-pentane 5.8 wt. % trans-pentane-2 1.6 wt. % cis-pentane-2 1-.5 wt. % 2-methyl butene-2 4.1 wt. % trans-piperylene 16.3 wt. % cis-piperylene 10.8 wt. % cyclopentene 10.1 wt. % dieye1opentadiene 34.0 wt. % cyclopentadiene/isoprene C 10 3.4 wt. % remainder 12.4 wt. % During the addition time, the temperature was in the 38°C to 45°C range. The reaction mass was heated to 145°C over 5 hours (18000 s). During this time 36 gms of unreacted hydrocarbon was removed. After 2 hours (7200 s) of slight vacuum, an additional 431 gms of hydrocarbon toluene and phenol were removed. Full vacuum at 210°C resulted in an additional distillate of 565 gms of phenol and C 5 alkylated phenol. The resultant product is further described in Table I. Example 12 — (Phenolic Resin Prep) To a reactor equipped as in Example 1 were added 1698.3 gms (18 moles) of phenol and 12.6 gms of BF 3 etherate in 10 gms of carbon tetrachloride. With the reactor temperature at 65°C, 408 gms (3 moles) of piperylene dimer were added to the reactor over 1 hour OMPI and 28 minutes (5280 s). The piperylene dimers used in this synthesis are believed to be a mixture of cyclic and linear products. The temperature range during the piperylene dimer addition was 65°C to 85°C. The reaction mass was heated to 150°C over 5 hours and 15 minutes (18900 s). The reaction continued for 2 hours (7200 s) at that temperature, after which, vacuum distillation was started. The resin was finished at 220°C and <2 mm of mercury (<0.2 kPa). The total distillate was 1694 gms. The resultant product is further described in Table I. Example 13 — (Phenolic Resin Prep) To a reaction vessel equipped as in Example 1 were added 1882 gms (20 moles) of phenol, 300 grams of toluene and 10.5 gms of BF g etherate in 10 gms of carbon tetrachloride. At a temperature of 39°C, slow addition of a piperylene concentrate, with the following composition, was begun. trans-pentene-2 2.2 wt. % cis-pentene-2 2.4 wt. % 2-methyl butene-2 5.4 wt. % trans-piperylene 31.0 wt. % cis-piperylene 19.6 wt. % cyclopentadiene 1.4 wt. % cyclopentene 23.0 wt. % dicyclopentadiene 1.4 wt. % remainder 13.6 wt. % The total addition time was 3 hours and 35 minutes (12900 s) over a temperature range of 33°C to 43°C. The reactants were then heated to 140°C over a 3 hour (10800 s) time period during which time unreactive ΓRE lights and some toluene were removed. An additional 3 hours (10800 s) reaction time at 145°C was given and vacuum distillation started. The resin was finished at 235°C and <2 mm of mercury (<0.3 kPa). See Table I for results. Example 14 — (Phenolic Resin Prep) To a reaction vessel equipped as in Example 1 was added 975.2 gms (8 moles) of 2,6 dimethyl phenol (98.5 percent purity with the remainder being mainly. meta and para cresol). The xylenol was heated to 70°C where 7.5 gms of BF 3 gas was added over 47 minutes (2820 s). Slow addition of 528 gms of oligomer of dicyclopentadiene (Oligomer Prep A), believed to have a molecular weight of 190, was conducted over a 3 hour (10800 s) period within the temperature range of 70°C to 80°C. 200 Grams of toluene was used to wash residual oligomer from the dropping funnel into the reactor. The reaction mass was heated to 160°C over a 6-hour (21600 s) period during which time most of the toluene was removed from the reactor via atmospheric distilla¬ tion. Vacuum stripping was started at 160°C. Distil¬ lation was finished at 220°C and <1 mm of Hg (<0.1 kPa). Analysis indicates formation of the bis xylenol of hydrocarbon oligomer with an average OH equivalent weight of 210. Thus the hydrocarbon molecular weight was 176. Xylenol recovery ratios confirm these values. See Table I for results. Example 15 — (Phenolic Prep) To a reactor equipped as in Example 1 were added 2258.4 gms (24 moles) of phenol and 264 gms (2 moles) of 99.9 percent reactive dicyclopentadiene concentrate (86.6 percent DCPD, 13.33 percent codimers and <0.1 percent lights). The reactor mass was heated to 48°C and addition of 5.1 gms of BF 3 gas was started. The reactor temperature, which rapidly rose to 70°C, was controlled with external cooling. The catalyst was added over a 7 minute (420 s) time period. The tempera¬ ture was then raised to 155°C over a 4 and 1/2 hour (16200 s) time period. Vacuum stripping was completed at 212°C and 1 mm of Hg (0.1 kPa). The resultant product is described in Table I. Example 16 — (Phenolic Prep) To a reactor equipped as in Example 1 were added 912 gms (4 moles) of bisphenol A, 1882 gms (20 moles) of phenol and 15.4 gms of BF 3 etherate. The reaction mass was heated to 83°C, where the addition of 1057 gms (8 moles) of 99.9 percent reactive dicyclo¬ pentadiene concentrate was begun- Addition was complete in 2 hours and 25 minutes (8700 s). The temperature range during addition was from 80°C to 85°C. The reaction was heated to 150°C over 6 hours (21600 s). Vacuum stripping was started at 150°C and finished at 215°C and 20 mm of Hg (2.7 kPa). See Table I for results. Example 17 — (Phenolic Prep) To a reactor equipped as in Example 1 were added 4140 gms (44 moles) of phenol and 18.6 gms of BF 3 etherate. The mass was heated to 58°C at which point 528 gms (2 moles) of oligomer, prepared as in Oligomer Prep B, and 400 gms of toluene were added. The tempera¬ ture at the end of the hydrocarbon addition period (1 hour, 17 minutes or 4620 s) was 80°C. The reaction was slowly heated to 155°C over 7 hours and 30 minutes (27000 s) at which point the excess phenol was removed. " OMPI The resin was finished at 225°C at less than 2 mm Hg (less than 0.3 kPa). The resultant product is described in Table I. OMPI TABLE I GPC Melt Ave, Functional Distribution, % Ave. Resin Eq. Wt. Pt. °C Funct. Lights 1 2 3 4 5 MW Example 1 241 59° 1.69 8.7 27.3 50.4 13.7 - - 392 Example 2 243 67° 1.91 - - 42.4 31.5 18.2 7.9 - - 456 Example 3 179 96° 2.65 1.9 4.4 49.5 25.7 15.2 4.4 469 Example 4 248 128° 2.48 - - 4.1 54.8 30.9 , 10.2 632 Example 5 176 109° 2.88 - - 3.0 41.6 27.1 21.4 6.9 522 Example 6 198 SS 1.90 - - 50.4 15.4 27.7 6.5 - - 365 Example 7 84 118° 4.56 - - 424 I N> Example 8 187 62° 2.08 - - 389 O I Example 9 173 105° 2.75 - - 0.8 49.9 28.0 16.5 4.8 490 Example 10 287 88° _ - Example 11 258 79° 2.54 3.8 56.5 24.3 13.0 2.4 394 Example 12 175 61° 1.98 - - 18.4 65.3 16.4 - - - - 344 Example 13 132 65° 2.36 64.2 35.8 - - - - 314 Example 14 210 a 105° 2.00 Example 15 167 90° 2.27 - - 3.8 71.6 17.6 7.0 - - 388 Example 16 190 a 76° - - Example 17 211 a 119° - _ a by OH analysis Example 18 — (Epoxy Prep) To a reactor equipped with a stirrer, condenser, nitrogen sparge, thermowell and addition funnel were added 878.5 gms (3.5 eq. ) of the phenolic resin prepared in Example 2, 880 gms of the methyl ether of propylene glycol, 3.0 gms of 50 percent NaOH, 17 gms of water and 1618.7 gms (17.5 moles) of epichlorohydrin. The solution was heated to 75°C. 700 Grams (3.5 moles) of 20 percent NaOH was added over a 1 hour and 12 minute (4320 s) period. The reaction was held at 75°C for an additional 55 minutes (3300 s). The resin was transferred to a separating funnel where the brine and resin layers were allowed to separate. The brine layer was discarded and the resin solution returned to and heated to 75°C. 175 Grams (0.875 moles) of 20 percent NaOH was added over a 27 minute (1620 s) period and then allowed to digest for an additional hour 3600 s). The resin was transferred to a separating funnel, the brine layer drawn off, washed with water and the water layer removed. The resin solution was returned to the reactor where the epichlorohydrin and the methyl ether of propylene glycol were removed by vacuum distillation. The resin was finished at 150°C and 2 mm of Hg (0.3 kPa). The resin was a semi-solid at room temperature with an epoxy equivalent weight of 367. Examples 19 thru 33 — (Epoxy Prep) Table II illustrates the results of epoxy resins prepared from different phenolic resins. The manner of preparation was essentially the same as in Example 18. Ϊ E TABLE II Add'n Time Phenolic % NaOH Hrs:Min Epi/OH MP Example Used 1st 2nd 1st 2nd Ratio Finish °C EEW 19 Ex. 3 20 20 1:10 0.40 5:1 150°C 55 274 20 Ex. 4 20 20 1:40 0:29 5:1 150°C 95 292 21 Ex. 8 20 20 1:36 0:26 3:1 142°C Semi.Sol. 335 22 Ex. 7 20 20 2:05 0:22 4:1 235°C Semi.Sol. 175 Similar to 23 Ex. 9 20 20 0:53 0:25 5:1 140°C 66 247 24 Ex. 9 20 20 1:53 0:40 2.5:1 155°C 73 270 I t 25 Ex. 10 20 25 1:38 0:35 5:1 140°C 69 472 t I 26 Ex. 9 25 25 1:32 0:28 1.5:1 185°C 86 352 NOTE: Compare 23, 24 and 26 for < ≥ffect cf epi ratio on same phenolic. 27 Ex. 21 22 25 0:55 0:28 4:1 155°C Semi.Sol. 222 28 Ex. 12 22 25 1:00 0:37 4:1 160°C Semi.Sol. 352 29 Ex. 13 22 25 1:10 0:22 5:1 140°C Semi.Sol. 256 30 Ex. 16 22 25 1:40 0:27 5:1 160°C Semi.Sol. 251 31 Ex. 14 22 25 1:03 0:33 5:1 170°C 77 325 32 Ex. 17 22 25 1:14 0:47 5:1 180°C 76 310 The resins prepared in Examples 18-32 were cured with 0.87 moles of Nadic methyl anhydride (maleic anhydride adduct of methyl cyclopentadiene) per epoxy equivalent and 1.5 weight percent of dimethyl amine based upon the weight of the epoxy resin employing the following cure schedule. 2 hours (7200 s) at 90°C 4 hours (14400 s) at 165°C 16 hours (57600 s) at 200°C The physical properties are provided in Table III. OMPI ^ ■ H M wo cn c^ oo c c y-t n co o m o e TH - a r^ D co cyi rH O in o rH H CM rH t-t rH rH i-H rH rH rH rH vo in co ro co co o in f* rH CM CM CM H 'φ O rH CO ' Cn c c-" CM o in < en in oo rH rH rH H CM O O CM rH CM iH CM rH rH O «4 * ' ' CM in CM tn CM rH rH cn _n en H H θ in v-3 σ rH co co cM r- oo in co .-*- i H vo o en oo m cM vo ιn ιn ιn <-_> m u. v-3 in m CO CO '!i " o CO cM H The shrinkage properties of Examples 19, 20 and 23 were compared to those of two conventional epoxy resins. Conventional Resin (CR) 1 was a phenol- -formaldehyde epoxy novolac resin having an average epoxide equivalent weight (EEW) of 178 and an average epoxy functionality of 3.8. Conventional Resin 2 was a diglycidyl ether of bisphenol A having an average EEW of 190. The resins were cured with 0.87 moles of Nadic methyl anhydride (maleic anhydride adduct of methyl- cyclopentadiene) per oxirane equivalents and 1.5 wt. percent benzyl dimethyl amine based on the epoxy resin, using the following cure schedule: 2 hrs. (7200 s) at 90°C 4 hrs. (14400 s) at 165°C 16 hrs. (57600 s) at 200°C The linear shrinkage in a 10" by 1" (25.4 cm x 2.54 cm) V shaped mold was determined by measuring the length of the specimen after cure. The results were as follows. % Shrinkage Resin During Cure CR 1 0.98 CR 2 0.99 Example 19 0.70 Example 20 0.75 Example 23 0.49 The temperature stability of the epoxy resins prepared in Examples 19 and 20 were compared to CR 1 employing the following procedure. Clear unfilled castings, 1/8" (0.3175 cm) in thickness, were prepared using the same formulation and cure schedule described in the shrinkage evaluation. 1" x 3" (2.54 cm x 7.62 cm) specimens were exposed to 260°C with the following results. % Wt. Loss after 100 hrs 1 300 hrs* 500 hrs 3 CR 1 2.56 3.38 3.87 Example 19 2.70 4.20 5.08 Example 20 2.46 3.52 4.23 Flexural Strength, psi/MPa after 100 hrs 1 300 hrs 2 500 hrs 3 CR 1 10,354/71.4 8,388/57.8 8,383/57.8 Example 19 9,970/68.7 6,694/46.2 6,360/43.9 Example 20 7,293/50.3 6,921/47.7 6,571/45.3 1 36 x 10* seconds 2 108 x 10 4 seconds 3 180 x 10 4 seconds The results show remarkably good temperature stability when compared to a well known high temperature stable epoxide. The chemical resistance of. the epoxy resins of Examples 19 and 20 were compared to that of CR 1 by exposing 1" x 3" (2.54 cm x 7.62 cm) specimens to various solvents at 23°C. The weight change was recorded after exposure at various times. The castings were prepared employing the same formulation and cure schedule as was employed in the shrinkage evaluation. The results are provided in Table IV. % Weight Gain After the Indicated Days 7 21 42 90 Acetone Cr 1 0.11 0.54 1.21 1.57 Example 19 3.01 7.96 13.80 21.57 Example 20 1.22 4.16 8.64 17.75 Water CR 1 0.32 0.56 0.74 0.90 Example 19 0.20 0.31 0.36 0.38 Example 20 0.17 0.30 0.34 0.40 3% H 2 S0 4 CR 1 0.30 0.52 0.69 0.84 Example 19 0.18 0.28 0.33 0.34 Example 20 0.16 0.26 0.32 0.38 10% NaOH Cr 1 0.22 0.38 0.49 0.58 Example 19 0.13 0.20 0.24 0.28 Example 20 0.10 0.18 0.23 0.28 10% HC1 CR 1 0.16 0.30 0.41 0.53 Example 19 0.12 0.20 0.23 0.25 Example 20 0.08 0.16 0.22 0.27 Example 33 — (Preparation of Solid Epoxy Resin Into a 5-necked, 1-liter glass reaction vessel equipped with a stirrer, condenser and tempera¬ ture controller were charged 65.4 parts (0.21 epoxy equivalent) of the epoxy resin prepared in Example 32 above and 14 parts (0.12 phenolic equivalent) of bisphenol A. After raising the temperature to 90°C, 0.07 part of ethyltriphenyl phosphonium acetete*acetic acid complex catalyst solution (70 percent in methanol) was added. The temperature was then increased to 175°C and maintained at this temperature for 1 hour (3600 s). The resultant solid epoxy resin had the following properties. EEW 768 Viscosity 6800 cps @ 175°C (6.8 Pa-s) Softening Point 137.7°C Example 34 — Preparation of Solid Epoxy Resin Into a reaction vessel equipped as in Example 33 was charged 75 parts (0.42 epoxy equivalent) of a diglycidyl ether of bisphenol A having an average epoxy equivalent weight of 179 and 57.4 parts (0.27 phenolic equivalent) of the phenolic composition prepared as in Example 17 above. After raising the temperature to 90°C, 0.08 part of ethyltriphenyl phosphonium acetate•acetic acid complex catalyst solution (70 percent in methanol) was added. The temperature was then increased to 175°C and maintained at this tempera¬ ture for 1 hour and 15 minutes (4500 s). The resultant solid epoxy resin had the following properties. EEW 778 Viscosity 7200 cps @ 175°C (7.2 Pa-s) Softening Point 127°C

Claims: 1. A composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule, which is substantially free of ether groups and which composition results from an acid catalyzed reaction of (A) at least one aromatic compound containing at least one aromatic hydroxyl-group and from one to two aromatic rings and at least one ortho or para position relative to a hydroxyl group available for ring alkylation; with (B) at least one unsaturated hydrocarbon wherein components (A) and (B) are employed in quanti¬ ties which provide a mole ratio of component (A) to component (B) of from 1.8:1 to 30:1 and wherein said catalyst is employed in a quantity of from 0.01 to 5 percent by weight based upon the weight of component (A), characterized in that component (B) is selected from (1) monounsaturated or diunsaturated hydrocarbons having from 4 to 6 carbon atoms or mixtures thereof; (2) unsaturated hydrocarbons containing an average of from 6 to 55 carbon atoms per molecule and containing not more than 94 weight percent dicyclopentadiene; (3) oligomers and/or cooligomers of hydrocarbon dienes, which dienes have from 4 to 18 carbon atoms and which dienes contain at least 6 percent by weight of dienes other than dicyclopentadiene; and (4) mixtures thereof. 2. The composition of Claim 1 characterized in that component (B) is a composition comprising from 20 to 94 percent by weight of dicyclopentadiene, from 1 to 30 percent by weight of dimers other than dicyclo¬ pentadiene and codimers of C -C5 hydrocarbons, from zero to 10 percent by weight of oligomers of C 4 -Cg dienes, and the balance, if any, to provide 100 percent by weight of C.-C 8 alkanes, alkenes and dienes. 3. The composition of Claim 2 characterized in that component (B) is a dicyclopentadiene concentrate containing from 70 to 94 percent by weight of dicyclo¬ pentadiene, from 6 to 30 percent by weight of dimers other than dicyclopentadiene and codimers of C.-C 6 hydrocarbons, from zero to 7 percent by weight of oligomers of C 4 -C & dienes, and the balance, if any, to provide 100 percent by weight of C . -C alkanes, alkenes and dienes. 4. The composition of Claim 2 characterized in that component (B) is a crude dicyclopentadiene stream containing from 20 to 70 percent by weight of dicyclopentadiene, from 1 to 10 percent by weight of dimers other than dicyclopentadienes and codimers of C 4 -C 6 hydrocarbons, from 0 to 10 percent by weight of oligomers of C 4 -C β dienes, the balance to provide 100 percent by weight of C 4 -C 8 alkanes, alkenes and dienes. 5. The composition of Claim 1 characterized in that component (B) is a crude piperylene or isoprene stream containing from 30 to 70 percent by weight of piperylene or isoprene, from zero to 10 percent by weight of CQ-CT ? timers an d codimers of C 4 -C 8 dienes, and the balance to provide 100 percent by weight of C 4 -Cg alkanes, alkenes and dienes. 6. The composition of Claim 1 characterized in that component (B) is an unsaturated hydrocarbon composition comprising from 90 to 100 percent by weight of the dimer of piperylene, from 0 to 10 percent by weight of higher molecular weight oligomers of pipery¬ lene, and from 0 to 4 percent by weight of piperylene. 7. The composition of Claim 1 characterized in that component (B) contains an unsaturated hydrocarbon prepared by the oligomerization of dicyclopentadiene concentrate, which oligomerization product contains an average of from 12 to 55 carbon atoms per molecule. 8. An epoxy resin composition resulting from the dehydrohalogenation of the reaction product of (C) an epoxy alkyl halide with (D) a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule, wherein components (C) and (D) are employed in quantities which provide a ratio of epoxy groups to phenolic hydroxyl groups of from 1.5:1 to 20:1, charactetized in that component (D) is the composition of any one of Claims 1 to 7. OMPI 9. Solid compositions resulting from reac¬ tions in the presence of an effective quantity of a suitable catalyst, (I) at least one epoxy resin having an average of more than one 1,2-epoxy groups per mole¬ cule with (II) at least one material having an average more than one phenolic hydroxyl group per molecule, characterized in that component (II) is the phenolic hydroxyl-containing composition of any one of Claims 1 to 7. 10. The solid compositions of Claim 9 charac¬ terized in that component (I) is the epoxy resin compo¬ sition of Claim 8. 11. The solid compositions of Claim 9 charac¬ terized in that component (I) is the epoxy resin compo- sition of Claim 8, and component (II) is the phenolic hydroxyl-containing compoisition of any of Claims 1 to 7.

Inventors: NADERHOFF BRYAN A, NELSON DONALD L, NADERHOFF, BRYAN, A., NELSON, DONALD, L.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1983
Main classification: C08G59
IPC codes: C07C37, C07C39, C08G59, C08G61, C08G65, C08L63