NO162968B - PHENOLIC HYDROXYL-SUSTAINED RESINES AND USES OF THESE FOR THE PREPARATION OF EPOXY RESIN MATERIALS. - Google Patents

Description

The present invention relates to a phenolic resin and more

than one phenolic hydroxyl group and more than one aromatic ring per molecule, which is essentially free of ether groups and which phenolic resin is obtained by an acid-catalyzed reaction between

(A) at least one aromatic compound containing at least one aromatic hydroxyl group and from 1 to 2 aromatic rings

and at least one ortho or para position relative to one

hydroxyl group available for ring alkylation and

(B) at least one unsaturated hydrocarbon in which the constituents (A)

and (B) are used in amounts that give a molar ratio of

component (A) and component (B) of from 1.8:1 to 30:1 and in which said catalyst is used in an amount of from 0.01

to 5% by weight based on the weight of component (A), and

use thereof for the production of an epoxy resin material.

Epoxy resins have hitherto 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 have excellent properties, but in some cases they may have less than desired moisture or chemical resistance properties, electrical properties or low elongation values. Glycidyl ethers of polyhydric phenols obtained from monohydric phenols and dicyclopentadiene are disclosed in US Patent No. 3,536,734.

In addition to overcoming one or more of those in front

mentioned shortcomings, the epoxy resins obtained through the present invention in some cases have improved shape shrinkage properties and improved resistance to aqueous solvents.

The phenolic resin according to the present invention is characterized in that the component (B) comprises from 20 to 94 weight percent dicyclopentadiene, from 1 to 30 weight percent dimers different from dicyclopentadiene and codimers of C^-Cg hydrocarbons, from 0 to 10 weight percent oligomers of C4-Cg- dienes, and the remainder, if any, to give 100% by weight, C4-C6 alkanes, -alkenes and -dienes.

Another aspect of the present invention is its application

of the phenolic resin for the production of an epoxy resin material by dehydrohalogenation of the reaction product between an epoxy alkyl halide and said phenolic resin, in amounts which give

a ratio of epoxy groups to phenolic hydroxyl groups of from 1.5:1 to 20:1.

Solid resins are formed by reacting in the presence of an effective amount of a suitable catalyst, (I) at least one epoxy resin having an average of more than one 1,2-epoxy group per molecule and (II) at least one material with an average of more than one phenolic hydroxyl group per molecule,

wherein component (II) is the phenolic hydroxyl resin described above, or component (I) is the epoxy resin described above, or both components (I) and (II) are the resins described above.

Suitable aromatic hydroxyl-containing compounds that can be used herein include any such compound containing one or two aromatic rings, at least one phenolic hydroxyl group, and at least one ortho or para ring position to a hydroxyl group available for alkylation.

Particularly suitable, aromatic, hydroxyl-containing compounds that can be used here include, for example, phenol, chlorophenol, bromophenol, methylphenol, hydroquinone, catechol, resorcinol, guaiacol, pyrogallol, phloroglucinol, isopropylphenol, ethylphenol, propylphenol, p-butylphenol, isobutylphenol, octylphenol, nonylphenol, cumylphenol, p-phenylphenol, o-phenylphenol, m-phenylphenol, bisphenol A, dihydroxydiphenylsulfone and mixtures thereof.

Particularly suitable unsaturated hydrocarbons that can be used here include, for example, a dicyclopentadiene concentrate containing from 70 to 94 weight percent dicyclopentadiene, from 6 to 30 weight percent of dimers other than dicyclopentadiene and codimers of C4-Cg hydrocarbons such as e.g. cyclopentadiene-isoprene, cyclopentadiene-piperylene, cyclopentadiene-methylcyclopentadiene and/or dimers of isoprene, piperylene and methylcyclopentadiene, from 0 to 7% by weight of oligomers of C4~Cg-dienes such as e.g. C^-C^g trimers and the remainder if any, to give 100% by weight, of C4~Cg alkanes, alkenes and dienes such as butadiene, isoprene, piperylene, cyclopentadiene, cyclopentene, 2-methylbutene-2, cyclohexene, cyclohexadiene, methylcyclopentadiene and 1,5-hexadiene. Methods for producing these dicyclopentadiene concentrates and more detailed descriptions thereof can be found collectively in US patent no. 3,557,239 and US patent no. 4,167,542.

Particularly suitable unsaturated hydrocarbons which can also be used herein include a crude dicyclopentadiene stream containing from 20 to 70 weight percent dicyclopentadiene, from 1 to 10 weight percent dimers other than dicyclopentadiene and codimers of C4.-C6. hydrocarbons (described above), from 0 to 10% by weight oligomer of C4-Cg-dienes, and the rest to give 100%, C4~C6-alkanes,

-alkenes and -dienes.

Particularly suitable unsaturated hydrocarbons which can also be used herein include a crude piperylene or isoprene stream containing from 30 to 70 weight percent piperylene or isoprene, from 0 to 10 weight percent Cg-C12 dimers and codimers of C4-Cg dienes, and the remainder to give 100%, C4-C8 alkanes, alkenes and dienes.

Hydrocarbon oligomers produced by polymerization of the reactive components in the above-mentioned hydrocarbon streams are also particularly suitable, e.g. dicyclopentadiene concentrate, crude dicyclopentadiene, crude piperylene or isoprene, individually or in combination with each other or in combination with high purity diene streams.

Examples of such hydrocarbon mixtures include, for example, an unsaturated hydrocarbon mixture comprising from 90 to 100 percent by weight of the piperylene dimer, from 0 to 10 percent by weight of oligomers of higher molecular weight piperylene and from 0 to 4 percent by weight of piperylene, and an unsaturated hydrocarbon produced by oligomerization of dicyclopentadiene concentrate, which oligomerization product contains in average numbers of from 12 to 55 carbon atoms per molecule.

Suitable acid catalysts which can be used here include, for example, Lewis acids, alkyl, aryl and aralkyl sulphonic acids and -disulphonic acids of diphenyl oxide and alkylated diphenyl oxide, sulfuric acid and mixtures thereof.

Lewis acids such as BF^ gas, organic complexes of boron trifluoride such as e.g. the complexes formed with phenol, cresol, ethanol and acetic acid. Lewis acids that also

are suitable include aluminum chloride, zinc chloride and stannous chloride.

Catalysts which are also suitable include, for example, activated clays, silicon oxide and silicon oxide-alumina complexes.

Suitable epoxy alkyl halides that can be used here include those represented by the formula where each R independently of one another is hydrogen or an alkyl group with from 1 to 6 carbon atoms and X is a halogen atom.

Particularly suitable epoxy alkyl halides include, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, methylepichlorohydrin, methylepibromohydrin, methylepiiodohydrin and mixtures thereof.

The epoxy resins can be cured alone or in mixtures with other epoxy resins with well-known curing agents or with the reaction products between the phenols and the unsaturated hydrocarbons described herein or mixtures thereof with the well-known curing agents.

Suitable epoxy resins which can be used to produce solid resins include, for example, the glycidyl ethers of aliphatic and aromatic compounds which have an average of more than one glycidyl ether group per molecule. These epoxy resins include the glycidyl ethers of nepentyl glycols, dibromopentyl 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 used to prepare solid resins include, for example, resorcinol, catechol, hydroquinone, bisphenol A, tetrabromobisphenol A, phenol-formaldehyde condensation products, phenolically terminated reaction products between epoxy resins with an average of more than one glycidyl ether - group per molecule and a phenolic hydroxyl-containing compound with 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 US Patent Nos. 3,477,990, 3,949,855 and 3,931,109.

Suitable catalysts that can be used in the reaction between 1,2-epoxy-containing materials and phenolic, hydroxyl-containing materials include, for example, alkali metal hydroxides and phosphonium and ammonium compounds such as those mentioned in the above-mentioned reference manual and US patents 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 their anhydrides, polyhydroxyaromatic compounds and combinations thereof.

In the production of the phenolic resins according to the present invention which contain 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 carried out at temperatures of from 33 to 270°C, preferably from 33 to 210°C.

The examples that follow shall illustrate the present invention

OLIGOMER PRODUCTION A

To a Parr reactor equipped with a stirrer, a heater, temperature and pressure indicators was added 1600 g of dicyclopentadiene (DCPD) concentrate. (DCPD) concentrate contains between 80 and 85% DPCD, between 13 and 19% codimers of cyclopentadiene with other C^-Cg dienes and between 1.0 and 5% lighter compounds (C4-Cg mono-olefins and -di -olefins). The reactor was pressurized to 1480 kPa with nitrogen gas and heated to 185°C for 2 hours 20 minutes (8400 s). The maximum observed pressure was 1977 kPa. The heat was turned off, the reactor vented and the contents, a white slurry at room temperature, removed. The product was believed to be a mixture of C4-C8 dimers, trimers, tetramers and pentamers with an average molecular weight of 198.

OLIGOMER PRODUCTION B

To a Parr reactor equipped as in oligomer preparation A, 1600 g of a similar concentrate of dicyclopentadiene was added. The reactor was pressurized to 14 80 kPa and heated to 2 00°C, and held at this temperature for 2 hours

(7200 p.). The resulting product was a waxy solid at room temperature and was believed to be a mixture consisting primarily of C4-Cg trimers, tetramers, pentamers, and hexamers with an average molecular weight of 264.

EXAMPLE 1 (Preparation of Phenolic Resin)

To a reactor equipped with a stirrer, a condenser, a thermowell and a heater were added 846.9 g (9.0 mol) of phenol, 50 g of water and 5.0 g (0.6% based on phenol ) concentrated sulfuric acid. The contents of the reactor were heated to 124°C.

1.5 mol of hydrocarbon oligomer, which was prepared in the same way as in oligomer preparation A, but with a molecular weight of 214, was added to the reactor during a 1 hour period (3600 s). 50 g of toluene was used to wash oligomer particles from the dropping funnel. After 1 hour and 10 minutes (4200 s), the reaction temperature was set to 190°C and the vacuum distillation equipment was put in place. The distillation was carried out over a 3 hour period (10800 s) and ended at 210°C and 1 mm of mercury (0.1 kPa). The total

the distillate was 663.1 g, yielding a recovered product of 611.4 g. Table I describes further results of this synthesis.

EXAMPLE 2 (Preparation of phenolic resin)

To a reactor equipped as in example 1, 2258 g (24 mol) of phenol and 30.8 g of BFg etherate in 40 g of carbon tetrachloride were added. The reactor was heated to 73°C. During a period of 2 hours and 51 minutes (10260 s), with temperatures between 73 and 83°C, 824 g (4 mol) of an oligomer with the commercial designation RI-300 was added. RI-300, which is available from CXI Incorporated, is an oligomer believed to be made from primarily piperylene with minor amounts of cyclopentadiene, isoprene, butadiene, and methylcyclopentadiene. The calculated molecular weight is 206. After the oligomer addition was finished, the temperature was increased to 150°C in the course of 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 the distillation was started. The total distillate was 1830.4 g and the yield was 13 2 2.4 g. See Table I for further results of this synthesis.

EXAMPLE 3 (Preparation of phenolic resin)

To a reactor equipped as in example 1, 1693.8 g (18 mol) of melted phenol and 10.3 g of BF3 etherate in 10 g of carbon tetrachloride were added. The mass was heated to 70°C at which point slow addition of 599.4 g of dicyclopentadiene concentrate was started. (The DCPD concentrate contained 83% DCPD and 0.9% light compounds, the remainder being essentially mixed C4~Cg dienes.) After half of the dicyclopentadiene concentrate had been added, another 10.3 g of BF^ etherate in 10 g carbon tetrachloride added to the reactor. The total hydrocarbon addition time was 2 hours (7200 s) within a temperature range of 70-80°C. The reaction mass was heated to 155°C over a period of 5 hours and

39 minute period (20340 s). The reaction was maintained at 155°C

for 7 hours and 41 minutes (27660 s) at which time the distillation was started. The reaction was completed at 165°C and 1 mm Hg (0.1 kPa). The total distillate was 995 g yielding 1338.8 g. See Table I for further results of this synthesis.

EXAMPLE 4 (Preparation of phenolic resin)

To a reactor equipped as in example 1, 1974 g (21 mol) of melted phenol and 23.2 g of BF3 etherate in 60 g of carbon tetrachloride were added. At a temperature of 65°C, the addition of 924 g (3.5 mol) of a hydrocarbon oligomer prepared in a similar manner as in oligomer preparation B was started. 30 g of toluene and 30 g 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 - 84°C. When the addition was complete, the reaction mixture was heated to 160°C over a 6 hour 41 minute period (24060 s). After 5 hours (18000 s) at this temperature, vacuum distillation was started. The reaction was terminated at 200°C and 1 mm of mercury (0.1 kPa). Total distillate recovery was 1284 g giving a two-digit yield of 1757.2 g. See Table I for further results of this synthesis.

EXAMPLE 5 (Preparation of phenolic resin)

To a reactor equipped as in example 1, 1599.7 g (17 mol) of phenol and 9.0 g of BF3 etherate, 0.4% by weight based on the total expected addition, were added. The BF 2 etherate was mixed with 10 g of carbon tetrachloride before the addition. The catalyst and phenol were heated to 75°C and the slow addition of 647 g

(4.857 mol 99.1% C^Q reagent) dicyclopentadiene concentrate started. 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 carried out for a further 1 hour and 30 minutes (5400 s) before the start of vacuum distillation. The reaction was terminated at 250°C and 1 mm of mercury (0.1 kPa). Total distillate was 875 g for a yield of 1390.7 g. See Table I for further results of this synthesis.

EXAMPLE 6 (Preparation of phenolic resin)

By using the same molar ratio between phenol and hydrocarbon as in Example 5, the BF 2 etherate catalyst was reduced from 0.4% of the total weight to 0.1% of the total reactant weight. The warm-up cycles were about the same. Table I describes the results of

this synthesis.

EXAMPLE 7 (Preparation of phenolic resin)

To a reactor equipped in Example 1, 880.8 g (8.0 mol) of resorcinol and 4.6 g of BF 2 etherate in 5 g of carbon tetrachloride were added. The contents were heated to 110°C and 264 g (2.0 mol) of dicyclopentadiene concentrate was added over a period of 1 hour 25 minutes (5100 s). The reactor temperature was regulated to between 110 and 112°C. When the dicyclopentadiene addition was complete, the reactor was gradually heated to 160°C over a 4 hour (14400 s) period. After a further 1 hour (3600 s) the temperature was reduced and some water added. The water, which did not separate, and 350 g of resorcinol were removed by vacuum distillation. The resulting product was essentially a mixture of tetrafunctional and hexafunctional derivatives of resorcinol and C 8 -C 8 dienes. Additional results of this synthesis are described in Table I.

EXAMPLE 8 (Preparation of phenolic resin)

To a reactor equipped as in example 1, 2162 g (20 mol) of ortho-cresol and 12.9 g of BF3 etherate in 20 g of carbon tetrachloride were added. The mass was heated to 68°C. 1057 g (8.0 mol)

of a 99.9% reactive diene hydrocarbon stream containing 85% dicyclopentadiene was added over the next 4 hours and 8 minutes (14880 s). The reaction temperature during this time was maintained between 68 and 85°C. The reactor was slowly heated to 150°C over 6 hours (21600 s). The product was then vacuum distilled and 1111 g of ortho-cresol recovered. The resulting product was essentially the result of 2 moles of ortho-cresol reacting with 1 mole of diene hydrocarbon. Additional results are described in Table I.

EXAMPLE 9 (Preparation of phenolic resin)

To a reactor equipped as in example 1, 3387.6 g (36 mol) of melted phenol and 17.9 g of BF3 etherate in 10 g of carbon tetrachloride were added. The reactor was heated to 70°C and 1081.1 g (8.18 mol) of a 99.9% reactive dicyclopentadiene concentrate used in Example 8 was added over a 3 hour 14 minute period (11640 s). The temperature during this addition period was maintained between 70 and 85°C. After the hydrocarbon addition was complete, the mass was heated to 145°C over a period of 4 hours (14400 s). A further reaction time of 3 hours was given at this temperature and vacuum stripping of unreacted phenol commenced. The reaction was terminated at 223°C and 1 mm of mercury (0.1 kPa). The total distillate was 2160 g, giving a product yield of 2326.6 g. See Table I for further results of this synthesis.

EXAMPLE 10 (Preparation of phenolic resin)

To a reactor equipped as in example 1, 1854 g (9 mol of p-octyl-phenol (diisobutylphenol) and 11.6 g of BF3~ etherate in 20 g of carbon tetrachloride were added. The temperature was set to 80 C and 475.7 g of 99 .9% active DCPD concentrate was added over a period of 1 hour 46 minutes (6360 s). The reactor was heated from 90 to 165°C over a period of 8 hours (28800 s) and vacuum distillation started 85 g of unreacted hydrocarbon and 915 g of octylphenol were removed. The resulting product contained essentially 2 and 3 phenolic hydroxyls per molecule. See Table I for further results of the synthesis.

EXAMPLE 11 (Preparation of phenolic resin)

To a reactor equipped as in example 1, 1035.1 g (11 mol) of phenol and 9.5 g of BF3 etherate in 200 g of toluene were added. The temperature was set to 40°C. A crude hydrocarbon stream containing mainly alkanes, alkenes and dienes in the C^-C^Q range, 355.5 g (calculated at 3.33 moles of active product) was added during

7 hours and 3 minutes (25380 s). A summary analysis of this flow is as follows:

During the addition time, the temperature was in the range 38 - 45°C. The reaction mass was heated to 145°C within 5 hours (18000 s). During this time, 36 g of unreacted hydrocarbon was removed. After 2 hours (7200 s) of low vacuum, an additional 431 g of hydrocarbon, toluene and phenol were removed. Full vacuum at 210°C resulted in a further distillate of 565 g of phenol and C 1 -alkylated phenol. The resulting product is further described in Table I.

EXAMPLE 12 (Preparation of phenolic resin)

To a reactor equipped as in example 1, 1698.3 g (18 mol) of phenol and 12.6 g of BF3 etherate in 10 g of carbon tetrachloride were added. At a reactor temperature of 65°C, 408 g (3 mol) of piperylene dimer was 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 - 85°C. The reaction mass was heated to 150°C during 5 hours and 15 minutes (18900 s). The reaction was continued for 2 hours (7200 s) at this temperature, after which the vacuum distillation was started. The resin was finished at 220°C and <2 mm Hg

(<0.2 kPa). The total distillate was 1694 g. The resulting product is further described in Table I.

EXAMPLE 13 (Preparation of phenolic resin)

To a reaction vessel equipped as in example 1, 1882 g (20 mol) of phenol, 300 g of toluene and 10.5 g of BF3 etherate in 10 g of carbon tetrachloride were added. At a temperature of 39°C, a slow addition of a piperylene concentrate, with the following composition, was started.

The total addition time was 3 hours and 35 minutes (12900 s) within a temperature range of 33 - 43°C. The reactants were then heated to 140°C for 3 hours (10800 s) during which time unreactive light compounds and some toluene were removed. A further 3 hours (10800 s) reaction time at 145°C was given and vacuum distillation started. The resin was terminated at 235°C and <2 mm Hg (<0.3 kPa). Results can be seen in the table

IN.

EXAMPLE 14 (Preparation of phenolic resin)

To a reaction vessel equipped as in example 1, 975.2 g (8 mol) of 2,6-dimethylphenol (98.5% purity, the remainder being mainly meta- and para-cresol) were added. The xylenol was heated to 70°C where 7.5 g of BF3 gas was added during 47 minutes (2820 s). Slow addition of 528 g of dicyclopentadiene oligomer (Oligomer Preparation A), assumed to have a molecular weight of 190, was carried out over 3 hours (10800 g) within a temperature range of 70-80°C. 200 g of toluene was used to wash residual oligomers from the dropping funnel into the reactor. The reaction mass was heated to 160°C over 6 hours (21600 s), during which time most of the toluene was removed from the reactor by atmospheric distillation. Vacuum stripping was started at 160°C. The distillation was finished at 220°C and

<1 mm Hg (<0.1 kPa). Analysis indicated formation of the bis-xylenol of the hydrocarbon oligomer with an average OH equivalent weight of 210. Thus, the molecular weight of the hydrocarbon was 176. Xylenol recovery conditions confirm these values. The results can be seen in table I.

EXAMPLE 15 (Preparation of phenolic resin)

To a reactor equipped as in Example 1 was added 2258.4 g (24 mol) phenol and 264 g (2 mol) 99.9% reactive dicyclopentadiene concentrate (86.6% DCPD, 13.33% codimer and <0 .1% light compounds). The reactor mass was heated to 48°C and addition of 5.1 g of BF 2 gas was started. The reactor temperature, which quickly rose to 70°C, was regulated by external cooling. The catalyst was added over 7 minutes (420 s). The temperature was then raised to 155°C over 1 hour (16200 s). Vacuum stripping was completed at 212°C and 1 mm Hg (0.1 kPa). The resulting product is described in Table I.

EXAMPLE 16 (Preparation of phenolic resin)

To a reactor equipped as in example 1 was added

912 g (4 mol) of bisphenol A, 1882 g (20 mol) of phenol and 15.4 g of BF^ etherate. The reaction mass was heated to 83°C, where the addition of 1057 g (8 mol) of 99.9% reactive dicyclopentadiene concentrate was started. The addition was complete in 2 hours 25 minutes (8700 s). The temperature range during the addition was from 80 to 85°C. The reaction mixture was heated to 150°C

for 6 hours (21600 s). Vacuum stripping was started at 150°C and ended at 215°C and 20 mm Hg (2.7 kPa). Results can be seen in table I.

EXAMPLE 17 (Preparation of phenolic resin)

To a reactor equipped as in example/1, it was added

4140 g (44 mol) of phenol and 18.6 g of BF 2 etherate. The mass was heated to 58°C at which point 528 g (2 mol) of oligomer, prepared / as in oligomer preparation B, and 400 g of toluene were added. The temperature at the end of the hydrocarbon addition period (1 hour and 17 minutes or 4620 s) was 80°C. The reaction mixture was

slowly heated to 155°C over 7 hours 30 minutes (27000 s) at which point excess phenol was removed. The resin was finished at 225°C at less than 2 mm Hg (less than 0.3 kPa). The resulting product is described in Table I.

EXAMPLE 18 (Preparation of epoxy resin)

To a reactor equipped with a stirrer, condenser, nitrogen inlet, thermowell and addition funnel was added 878.5 g (3.5 eq) of the phenolic resin prepared in Example 2, 880 g of the methyl ether of propylene glycol, 3.0 g of 50% NaOH, 17 g of water and 1618.7 g (17.5 mol) of epichlorohydrin. The solution was heated to 75°C. 700 g (3.5 mol) of 20% NaOH was added in the course of 1 hour and 12 minutes (4320 s). The reaction mixture was held at 75°C for an additional 55 minutes (3300 s). The resin was transferred to a separatory funnel where the salt solution and resin layers were allowed to separate. The brine layer was discarded and the resin solution was returned to the reactor and heated to 75°C. 175 g (0.875 mol) of 20% NaOH was added over 27 minutes (1620 s) and then allowed to act for a further 1 hour

(3600 s) . The resin was transferred to a separatory 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 Hg (0.3 kPa). The resin was a semi-solid at room temperature with an epoxy equivalent weight of 367.

EXAMPLES 19 - 32 (Preparation of epoxy resin)

Table II illustrates the results of epoxy resins prepared from various phenolic resins. The procedure was essentially the same as in example 18.

The resins prepared in Examples 18 - 32 were cured with 0.87 mol Nadic methyl anhydride (maleic anhydride adduct of methyl cyclopentadiene) per epoxy equivalent and 1.5 weight percent dimethylamine based on the weight of the epoxy resin using the following curing program:

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 indicated in Table III.

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 novolak resin with an average epoxy equivalent weight (EEW) of 178 and an average epoxy functionality of 3.8. Conventional resin 2 was a diglycidyl ether of bisphenol A with an average EEW of 190. The resins were cured with 0.87 mol Nadic methyl anhydride (maleic anhydride adduct of methyl cyclopentadiene) per mol. oxirane equivalents and 1.5% by weight benzyldimethylamine based on the epoxy resin, using the following curing program:

2 hours (7200 s) at 90°C

4 hours (14400 s) at 165°C

16 hours (57600 s) at 200°C

The linear shrinkage in a 25.4 cm x 2.54 cm V-shaped mold was determined by measuring the length of the article after curing. The results were as follows.

The temperature stability of epoxy resins prepared in Examples 19 and 20 was compared to CR 1 using the following procedure.

Clear unfilled castings, which had a thickness of 0.3175 cm, were produced using the same composition and curing program described in the shrinkage evaluation. Articles of 2.54 cm x 7.62 cm were exposed to 260°C with the following results. 1 4

36 x 10 seconds

<2>108 x IO<4> seconds

<3>180 x IO<4> seconds

The results show remarkably good temperature stability when compared with a well-known, high-temperature-stable epoxy.

The chemical resistance of the epoxy resins of Examples 19 and 20 was compared to that of CR 1 by exposing 2.54 cm x 7.62 cm articles to various solvents at 23°C. The weight change was recorded after exposure for different times. The castings were produced using the same composition and the same hardening program as was used in the shrinkage assessment. The results are given in Table IV.

EXAMPLE 33 (Preparation of solid epoxy resin)

To a 5-neck, 1-liter glass reaction vessel equipped with a stirrer, condenser, and temperature controller was added 65.4 parts (0.21 epoxy equivalent) of the epoxy resin prepared in Example 32 above and 14 parts (0.12 phenol equivalent) of bisphenol A. After raising the temperature to 90°C, 0.07 part of a catalyst solution (70% in methanol) of ethyltriphenyl-phosphonium-acetate-acetic acid complex was added. The temperature was then increased to 175°C and held at this temperature for 1 hour (3600 s). The resulting solid epoxy resin had the following

properties.

EXAMPLE 34 Preparation of solid epoxy resin

To a reaction vessel equipped as in Example 33 was added 75 parts (0.42 epoxy equivalent) of a diglycidyl ether of bisphenol A with an average epoxy equivalent weight of 179 and 57.4 parts (0.27 phenol equivalent) of the phenol preparation prepared as in example 17 above. After raising the temperature to 90°C, 0.08 part of a catalyst solution (70% in methanol) of ethyltriphenyl-phosphonium-acetate•acetic acid complex was added. The temperature was then raised to 175°C and held at this temperature for 1 hour and 15 minutes (4500 s). The resulting solid epoxy resin had the following properties.

Claims (9)

1. Phenolic resin with more than one phenolic hydroxyl group and more than one aromatic ring per molecule, which is essentially free of ether groups and which phenolic resin is obtained by an acid-catalyzed reaction between (A) at least one aromatic compound containing at least one aromatic hydroxyl group and from 1 to 2 aromatic rings and at least one ortho or para position in relation to a hydroxyl group available for ring alkylation and (B) at least one unsaturated hydrocarbon in which components (A) and (B) are used in amounts giving a molar ratio between component (A) and component (B) of from 1.8:1 to 30:1 and wherein said catalyst is used in an amount of from 0.01 to 5% by weight based on the weight of component (A), characterized in that component (B) comprises (1) 20-94% by weight dicyclopentadiene, (2) 1-30% by weight of dimers other than dicyclopentadiene and codimers of C^Cg hydrocarbons, (3) 0-10 wt% oligomers of C4-C8 dienes, and (4) the remainder, if any, to give 100% by weight, C4-C6 alkanes, alkenes and dienes. 2. Phenolic resin according to claim 1, characterized in that component (B) is a dicyclopentadiene concentrate containing from 70 to 94% by weight of dicyclopentadiene, from 6 to 30% by weight of dimers other than dicyclopentadiene and codimers of C4-C6 hydrocarbons, from 0 to 7% by weight of oligomers of C4- C6 dienes, and the remainder, if any, to give 100% by weight, C4-C6 alkanes, alkenes and dienes. 3. Phenolic resin according to claim 1, characterized in that crude fraction (B) is a crude dicyclopentadiene stream containing from 20 to 70 wt% dicyclopentadiene, from 1 to 10 wt% dimers other than dicyclopentadienes and codimers of C4-C6 hydrocarbons, from 0 to 10 wt% oligomers of C4 -C6-dienes and the remainder to give 100% by weight, C4-C6-alkanes, -alkenes and -dienes. 4. Phenolic resin according to claim 1, characterized in that component (B) is a crude piperylene or isoprene stream containing from 30 to 70% by weight of piperylene or isoprene, from 0 to 10% by weight of Cg-C^ dimers °9 codimers of C4-C6 dienes, and the remainder to give 100% by weight, C4-C6 alkanes, -alkenes and -dienes. 5. Phenolic resin according to claim 1, characterized in that component (B) is an unsaturated hydrocarbon resin comprising from 90 to 100% by weight of piperylene dimers, from 0 to 10% by weight of piperylene oligomers with a higher molecular weight, and from 0 to 4% by weight of piperylene. 6. Phenolic resin according to claim 1, characterized in that component (B) contains an unsaturated hydrocarbon which is produced by oligomerization of dicyclopentadiene concentrate, which oligomerization product contains an average of from 12 to 55 carbon atoms per molecule. 7. Use of phenolic resin according to claims 1-6, for the production of an epoxy resin material by dehydrohalogenation of the reaction product between an epoxy alkyl halide and said phenolic resin, in quantities which give a ratio between epoxy groups and phenolic hydroxyl groups of from 1.5:1 to 20:1. 8. Use of phenolic resin according to claims 1-6, for the production of solid materials by reactions, in the presence of an effective amount of a suitable catalyst, between (I) at least one epoxy resin with an average of more than one 1,2-epoxy group per . molecule and (II) said phenolic resin. 9. Use according to claim 8, where component (I) is the epoxy resin material from claim 7.