EP0148817A4 - Zusammensetzungen eine phenolische hydroxylgruppe enthaltend sowie daraus hergestellte epoxyharze sowie daraus hergestellte feste zusammensetzungen. - Google Patents

Zusammensetzungen eine phenolische hydroxylgruppe enthaltend sowie daraus hergestellte epoxyharze sowie daraus hergestellte feste zusammensetzungen.

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Publication number
EP0148817A4
EP0148817A4 EP19830902389 EP83902389A EP0148817A4 EP 0148817 A4 EP0148817 A4 EP 0148817A4 EP 19830902389 EP19830902389 EP 19830902389 EP 83902389 A EP83902389 A EP 83902389A EP 0148817 A4 EP0148817 A4 EP 0148817A4
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percent
weight
dienes
composition
component
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EP0148817A1 (de
Inventor
Donald L Nelson
Bryan A Naderhoff
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Dow Chemical Co
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/205—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings
    • C07C39/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/205—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings
    • C07C39/225—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing six-membered aromatic rings and other rings, with unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes

Definitions

  • 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 dicyclopentadiene are described in U.S. Patent No. 3,536,734.
  • the epoxy resins of the present invention in some instances, have improved mold shrink properties and improved aqueous solvent resistance.
  • 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
  • component (B) at least one unsaturated hydrocarbon, wherein components (A) and (B) are employed in quantities 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
  • 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.
  • 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 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 6 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.
  • 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 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.
  • aromatic hydroxylcontaining compounds which can be employed herein include , for example, phenol, chlorophenol, bromophenol, methylphenol, hydroquinone, catechol, resorcinol, guaiacol, pyrogallol, phloroglucinol, isopropylphenol, ethylphenol, propylphenol, t-butylphenol, isobutylphenol, octylphenol, nonylphenol, cumylphenol, p-phenylphenol, o-phenylphenol, m-phenylphenol, bisphenol A, dihydroxydiphenyl 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 6 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 4 -C 5 dienes such as, for example, C 14 -C ⁇ a 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, cyclopen
  • 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 6 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 5 alkanes, alkenes and dienes.
  • 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 6 dienes, and the balance to provide 100 percent by weight of C 4 -C 6 alkanes, alkenes and dienes.
  • 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 combination with one another on in combination with high purity diene streams.
  • hydrocarbon compositions include, for example, 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 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.
  • Lewis Acids as BF 3 gas, organic complexes of boron trifluoride such as those complexes formed with phenol, cresol, ethanol, and acetic acid.
  • suitable Lewis acids include aluminum chloride, zinc chloride, and stannic chloride.
  • 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
  • each R is independently hydrogen or
  • epoxy alkyl halides include, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, methylepichlorohydrin, methylepibromohydrin, 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, hydroquinone, 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 hydroxylcontaining 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.
  • the reaction between the phenolic hydroxylcontaining compounds and the unsaturated hydrocarbons can be conducted at temperatures of from 33°C to 270°C, preferably from 33°C to 210°C.
  • DCPD dicyclopentadiene
  • DCPD concentrate contains between 80 and 85 percent DCPD, between 13 and 19 percent codimers of cyclopentadiene with other C 4 -C 6 dienes and between 1.0 and 5 percent lights (C 4 -C 6 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 6 dimers, trimers, tetramers and pentamers having an average molecular weight of 198.
  • 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 6 trimers, tetramers, pentamers and hexamers having an average molecular weight of 264.
  • Example 1 (Phenolic Resin Prep) To a reactor, equipped with a stirrer, condenser, 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) period. 50 Grams of toluene was used to wash oligomer particles from the dropping funnel.
  • Example 2 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
  • 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.
  • 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 distillate 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
  • 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 2 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.
  • Example 2 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 addition of 647 gms (4.857 moles of 99.1 percent C 1 0 reactives) 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
  • 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 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.
  • Example 2 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 containing 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 2 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.
  • Example 2 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
  • 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 10 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 :
  • Example 2 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 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 2 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.
  • 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 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 2 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.
  • Oligomer Prep A oligomer of dicyclopentadiene
  • 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 distillation. Vacuum stripping was started at 160°C. Distillation 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 2 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 dicyclopentadiene 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 2 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 temperature 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. 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.
  • 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.
  • 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.
  • Nadic methyl anhydride maleic anhydride adduct of methyl cyclopentadiene
  • Example 19 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:
  • Example 33 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 temperature for 1 hour and 15 minutes (4500 s). The resultant solid epoxy resin had the following properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP19830902389 1983-06-27 1983-06-27 Zusammensetzungen eine phenolische hydroxylgruppe enthaltend sowie daraus hergestellte epoxyharze sowie daraus hergestellte feste zusammensetzungen. Withdrawn EP0148817A4 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1983/000980 WO1985000173A1 (en) 1983-06-27 1983-06-27 Phenolic hydroxyl-containing compositions and epoxy resins prepared therefrom and solid compositions prepared therefrom

Publications (2)

Publication Number Publication Date
EP0148817A1 EP0148817A1 (de) 1985-07-24
EP0148817A4 true EP0148817A4 (de) 1985-11-21

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EP19830902389 Withdrawn EP0148817A4 (de) 1983-06-27 1983-06-27 Zusammensetzungen eine phenolische hydroxylgruppe enthaltend sowie daraus hergestellte epoxyharze sowie daraus hergestellte feste zusammensetzungen.

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EP (1) EP0148817A4 (de)
JP (1) JPS60501711A (de)
BR (1) BR8307740A (de)
DK (1) DK172761B1 (de)
NO (1) NO162968C (de)
WO (1) WO1985000173A1 (de)

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DE3785445T2 (de) * 1985-04-15 1993-07-29 Dow Chemical Co Laminate.
JPH0611782B2 (ja) * 1986-06-13 1994-02-16 新日鐵化学株式会社 エポキシ変性炭化水素樹脂の製造方法
US11884773B2 (en) * 2018-12-19 2024-01-30 Nippon Steel Chemical & Material Co., Ltd. Phenolic resin, epoxy resin, epoxy resin composition and cured product of same
US10961208B1 (en) 2019-12-24 2021-03-30 Chang Chun Plastics Co., Ltd. Product of glycidyl ether of a mono or polyhydric phenol

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GB1076031A (en) * 1964-04-24 1967-07-19 Carless Capel & Leonard Ltd Improvments in or relating to the reaction between conjugated diolefines and phenols
DE1495710A1 (de) * 1963-01-23 1969-08-14 Hoechst Ag Verfahren zur Herstellung flexibler Harze
US3639490A (en) * 1966-02-25 1972-02-01 Cosden Oil & Chem Co Heptyl phenol alkylation

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DE1495710A1 (de) * 1963-01-23 1969-08-14 Hoechst Ag Verfahren zur Herstellung flexibler Harze
GB1076031A (en) * 1964-04-24 1967-07-19 Carless Capel & Leonard Ltd Improvments in or relating to the reaction between conjugated diolefines and phenols
US3639490A (en) * 1966-02-25 1972-02-01 Cosden Oil & Chem Co Heptyl phenol alkylation

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See also references of WO8500173A1 *

Also Published As

Publication number Publication date
DK77285D0 (da) 1985-02-20
NO850776L (no) 1985-02-26
NO162968B (no) 1989-12-04
DK172761B1 (da) 1999-06-28
BR8307740A (pt) 1985-06-04
DK77285A (da) 1985-02-20
NO162968C (no) 1990-03-14
JPS60501711A (ja) 1985-10-11
EP0148817A1 (de) 1985-07-24
WO1985000173A1 (en) 1985-01-17

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