CA1216091A - Solid materials prepared from epoxy resins and phenolic hydroxyl-containing materials - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Solid compositions are prepared by-reacting (A) one or more materials containing an average of more than one 1,2-epoxy groups with (B) one or more materials containing an average of more than one phenolic hydroxy groups wherein at least one of (A) or (B) contains with respect to (B) or has been prepared from with respect to (A) a reaction product of (1) at least one aromatic compound having at least one aromatic ring, at least one aromatic hydroxyl group and which aromatic ring contains at least one ortho or para position which is capable of being alkylated and (2) at least one aliphatic or cycloaliphatic C4-C6 unsaturated hydro-carbon or a dimer, codimer, oligomer of cooligomer thereof.

Description

Z160~1 SOLID MATERIALS PREPARED FROM EPOXY RESINS AND
PHENOLIC HYDROXYL-CONTAINING MATERIALS

: The present invention concerns the solid reaction products of one or more 1,2-epoxy-containing materials with one or more phenolic hydroxyl-containing materials wherein at least one of such epoxy-containing materials or such phenolic hydroxyl-containing materials is, in the instance of the phenolic hydroxyl-containing material, or has been prepared from, in the case of the epoxy-containing material, the reaction product of a phenolic hydroxyl-containing material having at least one alkylatable ortho-or para hydrogen and an unsatu-rated hydrocarbon containing from 4 to 6 carbon atoms, dimers and oligomers thereof and mixtures thereof.

Solid reaction products of epoxy-containing compounds and phenolic hydroxyl-containing compounds have found utility in such applications as castings, moldings, coatings, and laminates.

The products of the present invention provide for such uses at a reduced cost without great sacrifices in physical or chemical properties and in some instances 30,396-F -1- ~

-2- lZ16091 provide for an improvement in higher temperature appli-cations as evidenced by an increase in the glass transition temperature (Tg).

The present invention concerns solid compo sitions resulting from reacting, in the presence of an effective quantity of suitable catalyst, (A) at least one material having an average of more than one 1,2-epoxy group per molecule, with (B) at least one material having an average of more than one phenolic hydroxyl-group per molecule;
wherein at least one of (A) or (B) contains, with respect to (B), or has been prepared from, with respect to (A), a reaction product of (1) at least one aromatic compound having at least one aromatic ring, at least one aromatic hydroxyl group and which aromatic ring contains at least one ortho or para position capable of being alkylated, and (2) at least one aliphatic or cycloaliphatic unsaturated hydrocarbon containing from 4 to 6 carbon atoms, dimers and oligomers thereof and mixtures thereof.

Suitable epoxy resins which can be employed herein include those glycidyl ethers of aliphatic and aromatic compounds having an average of more than one glycidyl ether group per molecule. Suitable such epoxy resins include the glycidyl ethers of neopentyl glycol, dibromoneopentyl glycol, polyoxypropylene glycol, 30,396-F -2-_3_ ~216091 resorcinol, catechol, hydroquinone, bisphenol A, phenol--formaldehyde condensation products, tetrabromobis-phenol A, and mixtures thereof.

Suitable phenolic hydroxyl-containing materials which can be employed herein 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 ~ne glycidyl ether group per molecule and a phenolic hydroxyl-containing compound having an average of more than one phenolic OH group per molecule, and mixtures thereof.

Suitable such epoxy resins and phenolic hydroxyl-containing materials are more fully described in HANDBOOK OF EPOXY RESINS, by Lee and Neville, McGraw-Hill, 1967, U.S. 3,948,855 issued to Perry, U.S.

3,477,99~ issued to Dante et al. and U.S. 3,931,109 issued to Martin.

Suitable aromatic hydroxyl-containing compounds which contain at least one aromatic ring, at least one phenolic hydroxyl group and at least one ortho or para ring position available for alkylation which can be employed herein include, for example, phenol, chlorophenol, bromophenol, methylphenol, hydro-quinone, catechol, resorcinol, guaiacol, pyro~allol,phloroglucinol, isopropyl phenol, ethyl phenol, t-butyl phenol, octyl phenol, nonyl phenol, cumyl phenol, p-phenyl phenol, m-phenyl phenol, bisphenol A, dihydroxy diphenyl sulfide, dihydroxy diphenyl sulfone, and mixtures thereof.

30,396-F -3-~4~ ~2~609~

Suitable unsaturated hydrocarbons which, either in a crude or purified state, can be employed herein include, for example, butadiene, isoprene, piperylene, cyclopentadiene, cyclopentene, 2-methyl butene-2, cyclohexene, cyclohexadiene, methyl cyclo-pentadiene, dicyclopentadiene, limonene, dipentene, linear and cyclic dimers of piperylene, methyl dicyclo-pentadiene, dimethyl dicyclopentadiene, norbornene, norbornadiene, ethylidine norbornene, and mixtures thereof. Also suitable unsaturated hydrocarbons include the other dimers, codimers, oligomers and cooli.gomers of the aforementioned unsaturated hydrocarbons. Particu-larly suitable unsaturated hydrocarbons which can be employed herein include, for example, a dicyclopenta-diene concentrate containing from 70 to 94 percent byweight of dicyclopentadiene; from 6 to 30 percent by weight of Cg-Cl2 dimers or codimers of C4-C6 dienes 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 C14-C18 trimers of C4-C6 dienes and from zero to 10 percent by weight of aliphatic diolefins such as, for example, piperylene, isoprene, 1,5-hexadiene and cyclic olefins such as cyclopentadiene, methyl cyclo-pentadiene, and cyclopentene. Methods of preparation for these dicyclopentadiene concentrates and more detailed descriptions thereof can-be found collectively in U.S. Patent 3,557,239 issued to Gebhart et al. and U.S. Patent 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 30,396-F ~4~

~5~ ~2~609~

percent by weight dicyclopentadiene, from 1 to 10 percent codimers and dimers of C4-C6 hydrocarbons (described above), from zero to 10 percent oligomers of C4-C6 dienes and the balance to provide 100 percent, C4-C6 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 piperylene or isoprene, zero to ten percent by weight Cg-Cl2 dimers and codimers of C4-C6 dienes, and the balance to provide 100 percent C4-C6 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.

Suitable acid catalysts which can be employed herein as a catalyst for reacting the phenolic hydroxyl-containing compound with the unsaturated hydrocarbons include, for example, Lewis Acids, alkyl, aryl and aralkyl sulfonic acids and sulfonic acids of diphenyl-oxide and alkylated diphenyloxide, and mixtures thereof.

Particularly suitable are such Lewis Acids as organic complexes of boron trifluoride such as those complexes formed with phenol, cresol, ethanol or acetic acid. Also suitable Lewis acids include aluminum chloride, zinc chloride, and stannic chloride.

30,396-F -5--6- 1 Z 1 6 0 9 ~

Also suitable as catalysts include, for example, activated clays, silica, and silica-alumina complexes.

Suitable catalysts which can be employed in the reaction of 1,2-epoxy-containing materials and phenolic hydroxyl-containing materials include, for example, alkali metal hydroxides, phosphonium and ammonium compounds such as those mentioned in the above referenced handbook and patents.

Suitable epoxy alkyl halides which can be employed herein include those represented by the formula R R H
X-C-~ -H wherein each R is independently hydrogen or 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 solid epoxy resins of the present invention can be prepared, if desired, in the presence of a suitable inert reaction medium.

The lower molecular weight solid products of the present invention and which contain an average of more than one glycidyl ether group per molecule can be cured with the conventional epoxy resin curing agents.
Particularly suitable curing agents include, for 30,396-F -6-_7_ lZ16091 example, ~rimary, secondary and tertiary amines, poly-carboxylic acids and anhydrides thereof, polyhydroxy aromatic compounds, and combinations thereof.

The high molecular weight products of the present invention can also be employed with the conven-tional curing agents, but can also be employed without curing in solvent coatings.

The products of the present inventi-on can be employed in the preparation of coatings, castings, moldings, and laminates.

The following examples are illustrative of the present invention but are not to be construed as to limiting the scope thereof in any manner. All parts are by weight unless otherwise indicated.

(A) Preparation of DCPD/Phenolic To a reactor equipped with a stirrer, condenser, thermowell and heater add 1882 gms (20 moles) of phenol and 8 gms (0.4 percent based on total weight) of boron trifluoride etherate. Heat to 70C and add 132 gms (~1 mole) of a C10 diene stream containing mainly dicyclo-pentadiene and cyclopentadiene-isoprene codimers over a 20 minute (1200 s) period. Increase the temperature to 150C over a 3 hour (10800 s) time period and hold for 3 hours ~10800 s). Distill off unreacted phenol with a finishing temperature of 210C and less than 5 mm Hg.
The recoveEed product is a dicylopentadiene bisphenol with an average functionality of 2.07.

30,396-F -7--8- 12~6091 (B) Preparation of Solid Epoxy Resin Into a 5-necked 1-liter glass reaction vessel equipped with a stirrer, condenser and temperature controller were charged 100 parts (0.53 epoxy equivalent) of a diglycidyl ether of bisphenol A having an average epoxide equivalent weight (EEW) of 187.8 and 61.5 parts (0.375 OH equivalent) of the phenolic compound prepared in A above. The contents were heated to 90~C and 0.15 parts of ethyltriphenyl phosphonium acetate acetic acid complex catalyst solution (70 weight percent-catalyst in methanol) was added. The contents were then heated to 125C and maintained thereat for 1.5 hours (5400 s).
The resultant epoxy resin had the following properties.

viscosity 9700 cps ~ 150C (9.6 Pa-s) sofiening point 117.2C

A. Preparation of DCPD/Phenolic The DCPD phenolic was that described in Example 1 A

B. Preparation of Epoxy Resin from_DCPD/Phenolic To a reactor equipped with a stirrer, condenser, nitrogen sparge, thermowell and addition funnel were added 805 gms (5 OH equivalents) of the DCPD phenolic described in Example 1-A, 900 gms of the methyl ether of propylene glycol, 20 gms of water, 2 gms of 50 percent NaOH and 2312.5 gms (25 moles) of epihalo-hydrin. The solution was heated to 70C. 909.1 Grams (5 moles) of 22 percent NaOH was added over a 2 hour and 37 minute (9420 s) time period. The reaction was held at 70C for an additional 52 minutes (3120 s).

30,396-F -8-lZ16091 The resin was transferred to a separating funnel where the brine and resin layers were allowed to separate.
The brine layer was discarded, the resin solution returned to the reaction flask, and 139 gms of the methyl ether of propylene glycol added. The mass was heated to 69C and 200 gms (1.25 moles~ of 25 percent NaOH was added over a 21 minute (1260 s) period and then allowed to react an additional 75 minutes (4500 s).
The resin was transferred to a separating funnel, the brine layer drawn off, washed with water and-the water layer removed. The resin was returned to the reactor where the methyl ether of propylene glycol and excess epichlorohydrin were removed by vacuum distillation.
The resin was finished at 155C and 3 mm Hg (4 kPa).
The resin was a semisolid at room temperature with an epoxy equivalent weight of 237.

C. Preparation of Solid Epoxy Resin Into a glass reaction vessel equipped as in Example 1-B were charged 125 parts (0.53 epoxy equiva-lent) o~ the epoxy resin prepared in Example 2-B and 40.4 parts (0.36 OH equivalent) of bisphenol A. After heating to 85C and adding 0.125 part of ethyltriphenyl phosphonium acetate-acetic acid catalyst solution (70 weight percent in methanol) the contents were heated to and maintained at a temperature of 175C for 45 minutes (2700 s). The resultant solid epoxy resin had the following properties.

viscosity 9000 cps @ 150C (9.0 Pa-s) softening point 119.2C

30,396-F -9--10- lZ~6 Into a glass reaction vessel described in Example 1-B were added 100 parts (0.42 epoxy equivalent) of the epoxy resin prepared in Example 2-B and 46.7 parts (0.36 phenolic OH equivalent) of the product prepared in Example l-A. After heating to 90C, 0.15 part of ethyltriphenyl phosphonium acetate acetic acid complex catalyst solution (70 weight percent in methanol) was added. The temperature was then increased to 170C and maintained thereat for 2 hours (7200 s). The resultant epoxy resin had the following properties.

viscosity 4700 cps @ 150C (4.7 Pa-s) softening point 122.2C

A. Preparation of DCPD/Phenolic To a reactor equipped as in Example 1-A were added 2B23 gms (30 moles) of phenol and 16.1 gms of BF3 etherate in 20 gms of carbon tetrachloride. The mass was heated to 55C and 1201.2 gms (9.09 moles) of a 99.9 percent reactive C10 hydrocarbon stream consisting mainly of dicyclopentadiene and cyclopentadiene isoprene codimers was added over a 4 hour (14400 s) period. The temperature of the reaction mass was 80C after the hydrocarbon addition period. The reactor was heated to 150C over a 7 hour (25200 s) period and a vacuum distillation begun. The reaction was finished at 245C
and 1 mm Hg (0.1 kPa). The resin had an eguivalent weight of 187, a melt point of 115C and an average functionality of 2.95.

30,396-F -10--11- lZ~6091 B. Preparation of Epoxy Resin To a reactor equipped as in Examplè 2-B were added 841.5 gms (4.5 equivalents) of the resin described in 4-A, 840 gms of the methyl ether of propylene glycol, 9.2 gms of 50 percent NaOH, 15 gms o~ water and 2081.2 (22.5 moles) of epichlorohydrin. The solution was heated to 70C. 900 Grams (4.5 moles~ of 20 percent NaOH
was added over a 98 minute (5880 s) period. The reaction was held at 70C for an additional hour (3600 s). The resin and brine were separated as in Example 2-B. The resin solution was returned to the flask and heated to 75C. 225 Grams (1.125 moles) of 20 percent sodium hydroxide was added o-~er a 19 minute (1140 s) period.
The resin was allowed to continue to digest for 66 minute~ (3960 s). The resin was finished in the manner described in Example 2-B. The final conditions were 165C and 1 mm Hg (0.1 kPaj. The resin had a melt point of 78C and an EEW of 256.

C. PreParation of Solid EpoxY Resin To a glass reaction vessel equipped as in Example l-B were added 154.4 parts (O.60 epoxy equiva-lent) of the epoxy resin prepared in 4-B and 25 parts (O.22 OH equivalent) of bisphenol A. After heating to 85C, 0.16 part of ethyltriphenyl phosphonium acetate-acetic acid catalyst solution (70 weight percent in methanol) was added. The temperature was then increased to 175C and maintained thereat for 45 minutes (2700 s). The resultant product had the following properties.

~EW 490 viscosity 4200 cps @ 175C (4.2 Pa s) 30,396-F -11--12- lZ16~91 EXAMPI.E 5 A. Preparation of DCPD/Phenolic Same as that prepared in Example 4-A.

B. Preparation of Solid Resin To a glass reaction vessel equipped as in Example 1-B were added 313.4 parts (1.676 OH equivalents) of the 2.95 functional DCPD/phenolic prepared in A
above and 50 parts (0.28 epoxy equivalents) of a digly-cidyl ether of bisphenol A having an epoxide-e~uivalent weight of 179. After heating to 105C, 0.42 part of ethyltriphenyl phosphonium acetate~acetic acid complex catalyst (70 weight percent in methanol) was added.
After the exotherm (~192C) had subsided, the temper-ature was maintained at 175C until the percent epoxide was <0.5 percent. The product had the following properties.

epoxy content 0%
viscosity 2100 cps @ 175C (2.1 Pa-s) softening point 130.7C
phenolic O~ 6.31%

A. Preparation of DCPD/Phenolic To a reactor equipped with a stirrer, thermo-well and heater, were added 3387.6 gms (36 moles) of molten phenol and 17.9 gms of BF3 etherate in 10 gms of carbon tetrachloride. The reactor was heated to 70C
and 1081.1 gms (8.18 moles) of DCPD concentrate was added over a 3 hour and 14 minute (11640 s) period.
(DCPD concentrate contains about 80 percent-85 percent dicyclopentadiene, 13 to 19 percent codimers of cyclo-pentadiene with other C4 and C6 dienes and 1.0 to 5 percent lights (C4-C6 mono-olefins and di-olefins).

30,396-F -12--13- 1 Z 1 6 O 9 ~

The temperature during this addition period was main-tained between 70~ and 85C. After the hydrocarbon addition was complete, the mass was heated to 145C
over a 4 hour (14400 s) time period. An additional reaction time of about 3 hours (10800 s) was given at that temperature and vacuum stripping of unracted phenol commenced. The reaction was finished at 223C
and 2 mm of mercury (O.3 kPa). Total distillate was 2160 gms providing a product yield of 2326.6 gms. The resultant product had an average phenolic hy~roxyl functionality of 2.75 and a melting point of 105C.

B. Preparation of EPoxy Resin from DCPD/Phenolic To a reactor equipped with a stirrer, condenser, nitrogen sparge, thermowell and addition funnel were added 836.6 gms (4.7 eq.~ of the phenolic resin prepared in Example 6-A above, 840 gms of the methyl ether of propylene glycol, 10.9 gms of 50 percent NaOH, 16 gms of water and 2173.8 ms (23.5 moles) of epichlorohydrin.
The solution was heated to 73C. 987 Grams (4.94 moles) of 20 percent NaOH was added over a 53 minute (3180 s) period. The reaction was held at 75C for an additional 87 minutes (5220 s). The resin was trans-ferred to a separating funnel where the brine and resin layers were allowed to separate. The brine layer was discarded and the resin solution was returned to the reaction vessel and heated to 73C. 235 Grams (1.175 moles) of 20 percent NaOH was added over a 25 minute (1500 s) period and then allowed to digest for an additional 70 minutes (4200 s). The resin was transferred to a separating funnel, the brine layer drawn off, the resin was 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 30,396-F -13--14~ 6 O 9 1 distillation. The resin was finished at 140C and about 2 mm of Hg (0.3 ~Pa). The resin had a melting point of 66C and an average epoxy equivalent weight of 247.

C. Preparation of Solid Epoxy Resin To a reactor equipped with a mechanical stirrer, thermowell, temperature recorder-controller and condenser were added 494 gms (2 eq) of dicyclo-pentadiene novolac epoxide prepared in Exampl-e 6-B
10- above, 271.8 gms (0.5 moles) of tetrabromo~isphenol A
and 50 gms of the methyl ether of propylene glycol.
The contents were heated to 115C. 0.35 Gram (500 ppm) of 70 percent solids in methanol of ethyltriphenyl phosphonium acetate was added and the temperature set at 125C. The reaction was allowed to exotherm to 150C over the next 20 minutes (1200 s). 100 Grams of the methyl ether of propylene glycol were added to reduce foaming. Some methyl ether of propylene glycol was removed by vacuum stripping at 160C to 165C. The finished resin had a solids content of 93.7 percent and an epoxide content of 5 percent. Theoretical is 5.3 percent. The polymer equivalent weight was 865.

A. Pre~aration of DCPD Oli~er To a Parr reactor equipped with a stirrer, hea~er, temperature and pressure indicators was charged 1600 grams of DCPD concentrate as employed in Example 6-A. The reactor was pressurized to 200 psig (1480 kPa), heated to 200C and maintained thereat for about 2 hours (7200 s). The resultant product was a waxy solid at room temperature and is believed to be a mixture consist-- ing primarily of C5 trimers, tetramers, pentam~rs and hexamers and having an average molecular weight of 264.

30,396-F -14--15- 1 2 1 6~ 9 B. Preparation of DCPD/Phenolic To a reactor equipped as in Example 6-A above were added 4140 gms (44 moles3 of phenol and 18.6 gms of BF3 etherate. The mass was heated to 58C at which point 528 gms (2 moles) of oligomer, prepared as in Example 7-A above, and 400 ~ms of toluene were added.
The temperature at the end of the hydrocarbon addition period (1 hour, 17 minutes or 4620 s) was 80C. The reaction was slowly heated to 155C over 7 hours and 30 minutes (27000 s) at which point the excess phenol was removed. The resin was finished at 225C at less than 1 mm Hg (<0.1 kPa). The resultant product had an average phenolic hydroxyl equivalent weight of 211 and a melting pcint of 119C.

C. Preparation of Epoxy Resin from DCPD/Phenolic To a reactor equipped with a stirrer, condenser, nitrogen sparge, thermowell and addition funnel were added 378.9 gms (1.8 eq.) of the phenolic resin prepared in Example 7-B above, 380 gms of the methyl ether of propylene glycol, 8 gms of water and 832 gms (9 moles) of epichlorohydrin. The solution was heated to 72C.
327.3 gms (1.8 moles) of 22 percent NaOH was added over a 1 hour and 14 minute (4440 s) period. The reaction was held at 70C for an additional 60 minutes (3600 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 the reactor and heated to 75C. 172 Grams (0.45 moles) of 25 percent Na~H was added over a 47 minute (2820 s) period and then allowed to digest for an additional hour (3600 s). The resin was trans-ferred to a separating funnel, the brine layer drawn off, washed with water and the water layer renloved.

30,396-F -15--16- 12~609~

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 180C and 5mm of Hg (0.7 kPa). The resin had a melting point of 76C and an average epoxy equivalent weight of 310.

D. Preparation of Solid Epoxy Resin Into a reactor equipped as in Example 1-B was added 65.4 parts of the epoxy resin prepared-in Example 7-C above and 14 parts of bisphenol A. After raising the temperature to 90C, 0.07 part of ethyltriphenyl phosphonium acetate-acetic acid complex catalyst solu-tion (70 percent in methanol) was added. The tempera-ture was then increased to 175C and maintained thereat for one hour (3600 s). The resultant solid epoxy resin had the following properties.

viscosity 6800 cps @ 175C (6.8 Pa~s) softening point 137.7C

Into a reaction vessel equipped as in Example 1 was charged 75 parts of a diglycidyl ether of bisphenol A
having an average EEW of 179 and 57.4 parts of a DCPD/-phenolic prepared as in E~ample 7-B above. After raising the temperature to 90C, 0.08 parts of ethyl~
triphenyl phosphonium acetate-acetic acid complex catalyst solution (70 percent in methanol) was added.
The temperature was then increased to 175C and 30,396-F -16--17- ~Z1609~

maintalned thereat for 1 hour and 15 minutes (4500 s).
The resultant solid epoxy resin had the following properties.

viscosity 7200 cps @ 175C (7.2 Pa-s) softening point 127C

30,396-F -17-

Claims (9)

1. Solid compositions resulting from reacting, in the presence of an effective quantity of a suitable catalyst, (I) at least one material 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 molecule;
wherein at least one of (I) or (II) contains with respect to (II) or has been prepared from with respect to (I) a reaction product of (A) at least one aromatic compound containing (1) at least one aromatic ring, (2) at least one aromatic hydroxyl group and (3) which aromatic ring has at least one ortho or para position capable of being alkylated, and (B) at least one unsaturated alipahtic or cycloalipahtic hydrocarbon containing 4 to 6 carbon atoms or one or more dimers or oligomers thereof, or mixtures thereof.

2. A composition of Claim 1 wherein component (I) contains an epoxy resin composition resulting from the dehydrohalogenation of the reaction product of (A) an epoxy alkyl halide; with (B) an acid catalyzed product resulting from reacting (1) at least one aromatic hydroxyl--containing compound having one aromatic ring and at least one ortho or para position with respect to a hydroxyl group available for ring alkylation; with (2) at least one unsaturated hydrocarbon selected from (a) unsaturated hydrocarbons having from 4 to 6 carbon atoms; or (b) dimers, codimers, oligomers or cooligomers of unsaturated hydrocarbons, which hydrocar-bons have from 4 to 6 carbon atoms; and wherein components (B-1) and (B-2) are employed in quantities which provide a mole ratio of (B-1) to (B-2) of from 1.8:1 to 30:1; and components (A) and (B) are employed in quantities which provide an epoxy group to phenolic hydroxyl group ratio of from 1.5:1 to 20:1.

3. A composition of Claim 2 wherein the mole ratio of component (B-l) to component (B-2) is from 1.8:1 to 20:1 and the epoxy group to phenolic hydroxyl group ratio provided by components (A) and (B) is from 3:1 to 5:1.

4. A composition of Claim 3 wherein component (A) is epichlorohydrin.

5. A composition of Claim 1, wherein component (II) contains a material which is an acid catalyzed product resulting from reacting (A) at least one aromatic compound containing at least one aromatic hydroxyl-group and at least one aromatic ring and at least one ortho or para position relative to a hydroxyl group available for ring alkyla-tion; with (B) at least one unsaturated hydrocarbon selected from (1) unsaturated hydrocarbons having from 4 to 6 carbon atoms; or (2) dimers, codimers, oligomers or co-oligomers of unsaturated hydro-carbons, which hydrocarbons have from 4 to 6 carbon atoms; and 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 quantities of from 0.01 percent to 5 percent by weight of the quantity of component (A);

6. A composition of Claim 5 wherein components (A) and (B) are employed in quantities which provides a mole ratio of (A) to (B) of from 1.8:1 to 20:1 and said catalyst employed in a quantity from 0.3 to 1 percent by weight of component (A).

7. A composition of Claims 2, 3 or 4 wherein component (B-1) is phenol and component (B-2) is a composition comprising (1) from 70 to 94 percent by weight of dicyclopentadiene;
(2) from 6 to 30 percent by weight of C10 dimers;
(3) from zero to 7 percent by weight of oligomers of C4-C6 unsaturated hydro-carbon; and (4) the balance, if any, to provide 100 percent by weight of C4-C6 alkanes, alkenes and dienes.

8. A composition of Claim 5 wherein component (A) is phenol and component (B) is a composition compris-ing (1) from 70 to 94 percent by weight of dicyclopentadiene;
(2) from 6 to 30 percent by weight of C10 dimers;
(3) from zero to 7 percent by weight of oligomers of C4-C6 unsaturated hydrocarbon;
(4) the balance, if any, to provide 100 percent by weight of C4-C6 alkanes, alkenes and dienes.

9. A composition of Claim 6 wherein component (A) is phenol and component (B) is a composition compris-ing (1) from 70 percent to 94 percent by weight of dicyclopentadiene;
(2) from 6 to 30 percent by weight of C10 dimers;

(3) from zero to 7 percent by weight of oligomers of C4-C6 unsaturated hydro-carbon; and (4) the balance, if any, to provide 100 percent by weight of C4-C6 alkanes, alkenes and dienes.