JPH07149913A - Production of epoxy resin composition - Google Patents

Abstract

PURPOSE: To obtain an epoxy resin having a high water resistance, chemical resistance, electric properties, or the like, through dehydrohalogenation of a reaction product of an epoxy alkyl halide with a specific composition which is a reaction product of a hydroxy group-containing aromatic compound and an unsaturated hydrocarbon.

CONSTITUTION: This epoxy resin is prepared through dehydrohalogenation of a reaction product of (a) an epoxy alkyl halide (e.g. epichlorohydrin) and (b) a composition having more than one phenolic hydroxyl groups and more than one aromatic rings per molecule. Components (a) and (b) are used at amounts which give a ratio between the epoxy group and the phenolic hydroxide group of from 1.5:1 to 20:1. The composition as the component (b) is prepared through acid-catalyzed reaction of (A) an aromatic compound having at least one aromatic hydroxy group, one or two aromatic rings and at least one ortho- or para-position for a hydroxyl group used in ring alkylation and (B) an unsaturated hydrocarbon.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

The present invention relates to phenolic hydroxyl-containing compositions, epoxy resins made therefrom, and solid compositions made therefrom. Traditionally, epoxy resins are made from the condensation products of aromatic hydroxyl-containing compositions with aldehydes and ketones. Commercially available high performance epoxy resins, such as phenol-formaldehyde resins, have excellent properties, but in some cases have poor water resistance or chemical resistance, or electrical properties, or elongation. Is small. Glycidyl ethers of polyhydric phenols derived from monohydric phenols and dicyclopentadiene are described in US Pat.
3,536,734. The epoxy resin of the present invention, in addition to overcoming one or more of the above mentioned disadvantages, improves mold shrinkage and water solvent resistance.

The present invention provides a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule, the composition being substantially free of ether groups and (A ) It contains at least one aromatic hydroxyl group and one or two aromatic rings, and has at least one ortho or para position with respect to the hydroxyl group available for ring alkylation, Made from an acid-catalyzed reaction of an aromatic compound with (B) at least one unsaturated hydrocarbon, in which component (A) and component (B) are combined with component (A) versus component (A). B) is used in an amount such that the molar ratio is 1.8: 1 to 30: 1, preferably 1.8: 1 to 20: 1, and the acid catalyst is 0.01 to 5 of component (A). %, Preferably 0.3 to 1% by weight Component (B) is used as follows: (1) Monounsaturated or diunsaturated hydrocarbons having 4 to 6 carbon atoms or mixtures thereof; (2) Average 6 to 55 carbon atoms per molecule. Unsaturated hydrocarbons containing and containing up to 94% by weight of dicyclopentadiene; (3) Diene having 4 to 18 hydrocarbons and at least 6% by weight of other dienes of dicyclopentadiene.
A hydrocarbon diene oligomer and / or cooligomer containing; and (4) a mixture thereof. Component (B) is preferably dicyclopentadiene 20-9.
4 _wt%, C of 4 -C ₆ hydrocarbons, other dimers and co-dimer _1-30% by weight from _{dicyclopentadiene,} 0-10 wt% oligomers of dienes C 4 -C _6,
And a balance, if at all, of C ₄ -C ₆ alkanes, alkenes and the balance to provide 100% by weight of the diene.

Further, the present invention provides a reaction product of (C) an epoxyalkyl halide with (D) a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule. Made from dehydrohalogenation, component (C) and component (D) have a ratio of epoxy groups to phenolic hydroxyl groups of 1.5: 1 to 20:
1, preferably used in an amount that is 3: 1 to 5: 1,
In addition, the present invention relates to an epoxy resin composition characterized in that the component (D) is as described above. The invention further relates to (I) at least one epoxy resin having an average of more than one 1,2-epoxy group per molecule in the presence of an effective amount of a suitable catalyst, and (II) one molecule. Is prepared by reacting at least one substance having an average of more than one phenolic hydroxyl group per unit, component (II) being a phenolic hydroxyl-containing composition as described above, or component (I) Is the above-mentioned epoxy resin, or the component (I) and the component (II) are the above-mentioned compositions. Suitable aromatic hydroxyl-containing compounds which can be used here include one or two aromatic rings, at least one hydroxyl group and at least one ortho or para group with respect to the hydroxyl group available for alkylation. All compounds that contain a ring position. Particularly suitable aromatic hydroxyl-containing compounds which can be used here are, for example:
Phenol, chlorophenol, bromophenol, methylphenol, hydroquinone, catechol, resorcin, guaiacol, pyrogallol, phloroglucin,
Isopropylphenol, ethylphenol, propylphenol, t-butylphenol, isobutylphenol, octylphenol, nonylphenol, cumylphenol, p-phenylphenol, o-phenylphenol, m-phenylphenol, bisphenol A, dihydroxy Diphenyl sulfone, and mixtures thereof.

Particularly suitable unsaturated hydrocarbons which can be used here are, for example, 70 to 94% by weight of dicyclopentadiene; for example cyclopentadiene-isoprene, cyclopentadiene-piperylene, cyclopentadiene-methylcyclopentadiene and / or isoprene, piperylene and methyl cyclopentadiene hydrocarbons _C 4 -C _6, such as dimers, other dimers and co-dimer 6-30% by weight from dicyclopentadiene; for _{example, C} 4 ~ such as trimer of C 14 _{-C 13} oligomer 0-7 wt% of a diene of C _6; and if even been made, such as butadiene, isoprene, piperylene, cyclopentadiene, cyclopentene, 2-methylbutene -2, cyclohexene, cyclohexadiene, methyl cyclopentadiene Emissions, and 1,5-alkanes _C 4 -C _6, such as hexadiene, alkenes and dienes 100
A dicyclopentadiene concentrate containing the balance to provide a weight percentage. For a method of making these dicyclopentadiene concentrates and further details thereof, see Gebhart et al., US Pat. 3,5
57,239, and Nelson, U.S. Pat. 4,167,542. Particularly suitable unsaturated hydrocarbons which are further used herein, the dicyclopentadiene 20-70 wt%; C ₄ other dimer and co-dimer 1-10% by weight from dicyclopentadiene hydrocarbon -C ₆ (above 0 to 10% by weight of C _{4 to} C ₆ diene oligomers; and C _{4 to} C _6.
Is a crude dicyclopentadiene stream containing the balance to provide 100% by weight of the alkane, alkene and diene. Furthermore, particularly suitable unsaturated hydrocarbons which can be used here are piperylene or isoprene 3
_0-70% by _weight, C 4 -C ₆ dienes _C 9 of _{-C 12} dimers and co-dimer 0-10% by weight, and _C 4 -C
₆ is a crude isoprene stream that is crude piperylene containing the balance to provide 100% by weight of the ₆ alkane, alkene and diene.

Furthermore, it is formed by polymerizing the reaction components in the above-mentioned hydrocarbon streams, such as dicyclopentadiene concentrate, crude dicyclopentadiene, crude piperylene or crude isoprene, either alone or in combination with each other in a high-purity diene stream. The hydrocarbon oligomers mentioned are also particularly suitable. Examples of such hydrocarbon compositions are, for example, 90 to 100 wt% piperylene dimer, 0 to 10 wt% polymeric piperylene oligomers, and 0 to 4 wt% piperylene, unsaturated hydrocarbon compositions; and Unsaturated hydrocarbons made by the oligomerization of dicyclopentadiene concentrates in which the oligomeric product contains an average of 15 to 55 carbon atoms per molecule.

Suitable acid catalysts which may be used herein are the Lewis acids, diphenyl oxides and alkylated diphenyl oxides alkyl, aryl and aralkyl sulfonic acids and disulfonic acids, sulfuric acid, and mixtures thereof. Particularly suitable are organic complexes of boron trifluoride, such as those formed by phenol, cresol, ethanol and acetic acid, Lewis acids such as BF ₃ gas. Further suitable catalysts are, for example:
Activated clay, silica and silica-alumina complex. Suitable epoxyalkyl halides that can be used herein have the general formula; (In the formula, each R is independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and X is halogen.)
Is represented by. Particularly suitable epoxyalkyl halides are, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, methylepichlorohydrin, methylepibromohydroline methylepiodohydrin and mixtures thereof. The epoxy resin of the present invention can be cured by itself using a known curing agent or by a mixture with another epoxy resin, and further by using a known curing agent,
It can be cured with the reaction products of the aforementioned phenols and unsaturated hydrocarbons or mixtures thereof.
Suitable epoxy resins that can be used to make the solid composition are, for example, glycidyl ethers of aliphatic and aromatic compounds having an average of more than one glycidyl ether group per molecule. These epoxy resins are neopentyl glycol, dibromo neopentyl glycol, polyoxypropylene glycol, resorcin, catechol, hydroquinone, bisphenol A, phenol formaldehyde condensate, tetrabromobisphenol A and glycidyl ethers of mixtures thereof.

Suitable phenol-containing substances which can be used to make the solid composition are, for example, resorcin, catechol, hydroquinone, bisphenol A, tetrabromobisphenol A, phenol-formaldehyde condensate, on average 1 per molecule. Terminal phenolic reaction products of epoxy resins having more than 1 glycidyl ether group and phenolic hydroxyl groups having an average of more than 1 phenolic hydroxyl group per molecule
It is a containing compound. For suitable epoxy resins, phenolic hydroxyl-containing substances and curing agents, see Lee, Neville, "HANDBOOK.
OF EPOXY RESINS "McCraw-H
ill, 1967 and US Patent No. 3,47
7,990: 3,949,855 and 3,931,1
09. Suitable catalysts that can be used in the reaction of 1,2-epoxy-containing materials with phenolic hydroxyl-containing materials are described in the aforementioned Handbook and US Pat. 3,477,990; 3,948,8
55 and 3,931,109, as well as alcar metal hydroxides, and phosphonium and ammonium compounds.

Particularly suitable curing agents are, for example, primary, secondary and tertiary amines, polycarboxylic acids and their anhydrides, polyhydroxyaromatic compounds, and
These are the blends. In making compositions of the invention containing an average of more than one phenolic hydroxyl group and more than one aromatic ring per molecule, the reaction of a phenolic hydroxyl-containing compound with an unsaturated hydrocarbon is It is carried out at 33 to 370 ° C, preferably 33 to 210 ° C.

The present invention will be described with reference to the following examples, but the scope of the present invention is not limited in any case. Oligomer production A Par with stirrer, heater, thermometer and pressure gauge
Dicyclopentadiene (DCPD) concentrate 1 in r reactor
600g was charged. For DCPD concentrate, DCPD8
0-85%, cyclopentadiene and other _C 4 -C ₆ dienes and the co-dimer 13-19% and lights _(C 4 -C
₆ monoolephin and diolephine) 1.0-5%. Reactor with nitrogen gas at 200 psig (1
It was pressurized to 400 Kpa) and heated at 185 ° C. for 2 hours and 20 minutes (8,400 seconds). Maximum gauge pressure is 272
psig (1977 Kpa). Then, the heating was stopped, the reactor was opened, and the white slurry-like contents were removed at room temperature. This product is C ₄ -C with an average molecular weight of 198.
It appears to be a mixture of ₆ dimers, trimers, tetramers and pentamers. Oligomer Preparation B The same Parr reactor as Oligomer A was charged with 1600 g of the same dicyclopentadiene concentrate. 20 reactors
The pressure was increased to 0 psig (1480 Kpa), heated to 200 ° C., and then maintained at that temperature for 2 hours (7200 sec). The product is a waxy solid at room temperature with an average molecular weight of 26
4 _primarily, trimers of C 4 -C _6, tetramers, appears to pentamers and hexamers.

Example 1 (made of phenolic resin
Concrete) stirrer, a condenser, phenol 846.9g the bath and reactor equipped with a heater (9.0 mol), water 5
0 g and 5.0 g of concentrated sulfuric acid (0.6 based on phenol)
%) Was charged. The contents of the reactor were heated to 124 °. 15 mol of a hydrocarbon oligomer having a molecular weight of 214, which was produced by the same method as the oligomer preparation A, was used for 1 hour
00 sec) was added to the reactor. 50 g of toluene was used to wash the oligomer particles in the dropping funnel. After 1 hour and 10 minutes (4200 seconds), the reaction temperature was set to 1
The temperature was raised to 90 ° C. and a vacuum distillation apparatus was attached. Distillation was carried out for 3 hours (10800 sec) and was completed at 210 ° C. The degree of vacuum was 1 mmHg (0.1 Kpa). 663.1 g of total distillate and 611.4 g of recovered product.
It was g. The results of this synthesis are shown in Table 1.

Example 2 (Production of phenol resin
Concrete) into the same reactor as in Example 1 phenol 2258g (24m
ol) and 308 g of BF ₃ etherate dissolved in 40 g of carbon tetrachloride. The reactor was heated to 73 ° C. Product name RI-300 oligomer 824g (4mo
1) at 73 to 83 ° C. for 2 hours and 51 minutes (20260se
RI-300, commercially available from CXI, added over c), is an oligomer believed to be made from a major amount of piperylene and minor amounts of cyclopentadiene, isoprene, butadiene and methylcyclopentadiene. The estimated molar molecular weight is 206. After the addition of the oligomer is completed, the temperature is kept for 3 hours and 20 minutes (12000 seconds).
To 150 °. Reaction time is 6 at 150 ° C
The time was 25 minutes (23100 sec), and the distillation was started thereafter. The total distillate was 1830.4 g, and the yield was
It was 1322.4 g. The results of this synthesis are shown in Table 1.

Example 3 (made of phenol resin
Construction) Wet phenol 169 into a reactor similar to that of Example 1 (D).
3.8 g (18 mol) and 10.3 g of BF ₃ etherate dissolved in 10 g of carbon tetrachloride were charged. After heating it to 70 ° C., dicyclopentadiene concentrate 59
The addition of 9.4 g was gradually started. (This DCPD concentrate was 83% DCPD, 0.9% light-the balance was mainly mixed C _{4 to} C ₆ dienes.) After addition of 1/2 of the dicyclopentadiene concentrate, carbon tetrachloride was further added. 10 g
10.3 g of BF ₃ etherate dissolved in was added to the reactor. The total hydrocarbon addition time was 2 hours (7200 seconds) at 70 to 80 ° C. Then the reaction mixture is cooled to 155 ° C.
The heating was continued for 5 hours and 39 minutes (20340 seconds). The reaction was held at 155 ° C. for 7 hours and 41 minutes (27660 seconds), and then distillation was started. Distillation is 1mmHg at 165 ℃
(0.1 Kpa). The total distillate is 995g,
The yield was 1338.8. The results of this synthesis are shown in Table 1.

Example 4 (made of phenol resin
Construction) Wet phenol 197 to reactor similar to Example 1 (D)
4 g (21 mol) and 23.2 g of BF ₃ etherate dissolved in 60 g of carbon tetrachloride were charged. After reaching 65 ° C., 924 g (3.5 mol) of the hydrocarbon oligomer prepared by the same method as in the oligomer production B was added. Toluene 30g and carbon tetrachloride 30 as cleaning solvent
and g were added to the oligomer. Oligomer addition time is 65 hours to 84 degrees Celsius, 5 hours and 8 minutes (184808 seconds)
It was. After the addition was complete, the reaction was heated at 160 ° C. for 6 hours 41 minutes (24060 sec). Vacuum distillation was started after 5 hours (18000 sec) at that temperature. The distillation was completed at 200 ° C. and 1 mmHg (0.1 Kpa).
The total distillate was 1284 g and the total yield was 1757.2 g. The results of this synthesis are shown in Table 1.

Example 5 (Production of phenol resin
Structure) To reactor similar to that in Example 1 phenol 1599.7
g (17 mol) and 9.0 g of BF ₃ etherate, that is, 0.4% by weight of the total planned amount were charged. BF ₃ etherate was mixed with 10 g of carbon tetrachloride before charging. After heating the catalyst and phenol to 75 ° C., 647 g of dicyclopentadiene concentrate (98.7% C ₁₀ reactive 4.857 mol) was slowly added. Total addition time is 75-85 ° C for 2 hours 43 minutes (9780 seconds)
It was. After the addition of hydrocarbons, the temperature is changed to 4 hours (144
The temperature was gradually raised to 150 ° C. over 00 sec.
After continuing the reaction for another 1 hour and 30 minutes (5400 seconds),
Vacuum distillation was started. Distillation at 250 ℃, 1mmHg
It finished at (0.1 Kpa). The total distillate is 875g,
The yield was 1390.7 g. The results of this synthesis are shown in Table 1.

Example 6 (Production of phenol resin
Production) The same moles of phenol and hydrocarbon as in Example 5 were used, but the BF ₃ etherate catalyst was 0.4 based on all reactants.
The reaction was carried out at a reduction of from 0.1% by weight to 0.1% by weight.
The heating cycle was similar. The results are shown in Table 1.

Example 7 (Production of phenol resin
Structure) Reactor similar to that of Example 1 880.8 g of hellezilcin
(8.0 mol) and BF dissolved in 5 g of carbon tetrachloride
4.6 g of ₃ etherate was charged. 110 ° C of contents
After heating up to 264 g of dicyclopentadiene concentrate
(2.0 mol) was added over 1 hour and 25 minutes (5100 sec). The reaction temperature was controlled at 110 to 112 ° C. After the completion of the addition of dicyclopentadiene, the reactor was gradually heated to 160 over 4 hours (14400 seconds).
Heated to ° C. After another hour (3600 sec), the temperature was lowered and some water was added. The water which did not separate and 350 g of resorcinol were removed by vacuum distillation. The reaction product, Atsuta predominantly a mixture of tetrafunctional and hexafunctional derivatives and C ₉ -C ₁₁ dienes resorcinol.
The results are shown in Table 1.

Example 8 (made of phenol resin
Structure) To a reactor similar to that of Example 1, orthocresol 21
62 g (20 mol) and 12.9 g of BF ₃ etherate dissolved in 20 g of carbon tetrachloride were charged. 1057 g of a 99.9% reactive diene hydrocarbon stream containing 85% dicyclopentadiene heated to 68 ° C.
(8.0 mol) was added over 4 hours and 8 minutes (14880 sec). During this time, the reaction temperature was maintained at 65 to 85 ° C. The reactor was then allowed to cool for 6 hours (21600se
Heated to 150 ° C. over c). The product was then subjected to vacuum distillation to recover 1111 g of ortho-cresol. The product was mainly 2 mol of ortho-cresol reacted with 1 mol of diene hydrocarbon. The results are shown in Table 1.

Example 9 (Production of phenol resin
Manufacturing) To a reactor similar to that of Example 1, wet phenol 3387.
6 g (36 mol) and 17.9 g of BF ₃ etherate dissolved in 10 g of carbon tetrachloride were charged. 7 reactors
After heating to 0 ° C., 1081.1 g (8.18 m) of the 99.9% reactive dicyclopentadiene concentrate used in Example 8.
ol) was added over 3 hours and 14 minutes (11640 seconds). During this addition time, the temperature was maintained at 70 to 85 ° C. After the addition of hydrocarbons was completed, the reaction was allowed to run for 4 hours (14400
sec) and heated to 145 ° C. After reacting at that temperature for 3 hours (10800 seconds), unreacted phenol was removed by vacuum. Distillation is 223 ℃, 1mmH
It ended with g (0.1 Kpa). Total distillate is 2160
The yield was 2326.6 g. The results are shown in Table 1.

Example 10 (made of phenol resin
Preparation ) To a reactor similar to that of Example 1, BF ₃ etherate 1 dissolved in 1854 g (9 mol) of p-octylphenol (diisobutylphenol) and 20 g of carbon tetrachloride.
1.6 g was charged. After setting the temperature to 80 ° C., 99.
475.7 g of 9% active DCPD concentrate was added over 1 hour and 46 minutes (6360 seconds). Then, the reactor was heated from 90 ° C to 165 ° C for 8 hours (28800 sec).
After heating by heating, vacuum distillation was started. Then, 85 g of unreacted hydrocarbon and 915 g of octylphenol were removed. The products are mainly 2 and 3 per molecule.
It contained 1 phenolic hydroxyl group. The results are shown in Table 1.

Example 11 (made of phenol resin
Structure) To reactor similar to that in Example 1, phenol 1035.1
g (11 mol) and B dissolved in 200 g of toluene
9.5 g of F ₃ etherate was charged. The temperature was set to 40 ° C. Alkanes of mainly _C 5 _{~C 10,} alkenes,
Hydrocarbon stream 355.
5 g (estimated to be 3.33 mol of active product) were added over 7 hours and 3 minutes (25380 sec). The analytical values of this stream are shown below. n-Pentane 5.8 wt% t-pentane-2 1.6 〃 c-pentane-2 1.5 〃 2-methylbutene-2 4.1 〃 t-piperylene 16.3 〃 c-piperylene 10.8 〃 cyclopentene 10.1 〃 Dicyclopentadiene 34.0 〃 Cyclopentadiene / isoprene C ₁₀ 3.4 〃 Remainder 12.4 〃 The temperature was maintained at 38 to 45 ° C. The reaction was then heated at 145 ° C. for 5 hours (18000 sec). During this period, 36 g of unreacted hydrocarbon was removed. After slightly depressurizing for 2 hours (7200 seconds), further hydrocarbon toluene and 431 g of phenol were removed. Then, the pressure was sufficiently reduced at 210 ° C., and then phenol and C _{5 were} added.
565 g of alkylphenol was distilled off. The results are shown in Table 1.

Example 12 (made of phenol resin
Structure) To reactor similar to that in Example 1 phenol 1698.3
g (18 mol) and B dissolved in 10 g of carbon tetrachloride
12.6 g of F ₃ etherate was charged. After adjusting the reactor temperature to 65 ° C., 408 g of piperylene dimer (3 mo
1) was added to the reactor over 1 hour 28 minutes (5280 sec). The piperylene dimer used in this synthesis is believed to be a mixture of cyclic and linear products. The temperature during the addition of piperylene dimer was 65 to 85 ° C. The reaction was then heated to 150 ° C. for 5 hours and 15 minutes (18900 seconds). After continuing the reaction for 2 hours (7200 seconds) at that temperature, vacuum distillation was started. The resin distillation is 220 ℃, <2mmHg (<0.2Kp
It ended in a). The total distillate was 1694 g. The results are shown in Table 1.

Example 13 (made of phenol resin
Construction) Into a reaction vessel similar to that of Example 1, 1882 g of phenol
(20 mol), 300 g of toluene, and 10.5 g of BF ₃ etherate dissolved in 10 g of carbon tetrachloride were charged. At 39 ° C., a piperylene concentrate of the following composition was added lightly. t-Pentene-2 2.2% by weight c-Pentene-2 2.4 〃2-Methylbutene-2 5.4 〃t-Piperene 31.0 〃c-Piperene 19.6 〃Cyclopentadiene 1.4 〃Cyclopentene 23 0.0 〃 Dicyclopentadiene 1.4 〃 Remainder 13.6 〃 Total addition time is 3 hours and 35 minutes at 33 to 43 ° C (1290
It was 0 sec). The reaction was then heated at 140 ° C. for 3 hours (10800 sec). In the meantime, unreacted light components and some toluene were removed. 145 more
After continuing the reaction at C for 3 hours (10800 sec), vacuum distillation was performed. The resin distillation is 235 ° C <2mmHg
It ended with (<0.3 Kpa). The results are shown in Table 1.

Example 14 (Production of phenol resin
Concrete) was charged with 2,6-dimethyl phenol to the similar reaction vessel as in Example 1 (purity with the remainder primarily 98.5% meta and para-cresol) 975.2g (8ml). Xylenol and 7.5 g of BF ₃ for 47 minutes (282
0 sec) and heated to 70 ° C. Molecular weight 19
Dicyclopentadiene oligomer considered to be 0 (oligomer production A) (528 g) at 70 to 80 ° C. for 3 hours (1
It was added slowly over 0800 sec. To remove residual oligomer in the dropping funnel of the reactor, add toluene 200
g was used. The reaction was heated to 160 ° C. for 6 hours (21600 sec). Meanwhile, a large amount of toluene was removed from the reactor by atmospheric distillation. Distillation started at 160 ° C. Distillation is 220 ° C., <1 mmHg (<0.
1 Kpa). According to the analysis, the average OH equivalent is 21.
The formation of 0 hydrocarbon oligomer pi-xylenol was shown. The molecular weight of this hydrocarbon was 176. The xylenol recovery rate proved these values. First result
Shown in the table.

Example 15 (made of phenol resin
Structure) To a reactor similar to that in Example 1 phenol 2258.4
(24 mol) and 99.9% reactive dicyclopentadiene concentrate (DCPD 86.6%, codimer 13.
33% and light <0.1%) 264g (2mo
I) was charged. After heating the reaction to 48 ° C. BF ₃ 5.
1 g was added. The reaction temperature was rapidly raised to 70 ° C and controlled by external cooling. The catalyst was added over 7 minutes (420 sec). Then set the temperature to 4
The temperature was raised to 155 ° C. over 1/2 hour (16200 seconds). Vacuum distillation is performed at 212 ° C 1mmHg (0.1K
Pa). The results are shown in Table 1.

Example 16 (Production of phenol resin
Construction) To a reactor similar to that of Example 1 Bisphenol A912
g (4 mol), phenol 1882 g (20 mol)
And 15.4 g of BF ₃ etherate were charged. After warming the reaction to 83 ° C., 1057 g (8 mol) of 99.9% reactive dicyclopentadiene concentrate was added. The addition time was 2 hours and 25 minutes (8700 seconds). The temperature at the time of addition was 80 to 85 ° C. The reaction was heated to 150 ° C. for 6 hours (21600 sec). Vacuum distillation starts at 150 ° C and begins at 215
The test was completed at 20 ° C. and 20 mmHg (2.7 Kpa). The results are shown in Table 1.

Example 17 (Production of phenol resin
Phenol 4140g to similar reactor as granulation) Example 1
(44 mol) and 18.6 g of BF ₃ etherate were charged. Raise the contents to 58 ℃ and prepare oligomer B
528g (2mol) of oligomer prepared as
And 400 g of toluene were added. The temperature at the end of the addition of hydrocarbons (1 hour 17 minutes or 4620 seconds) was 80 ° C. The reaction was allowed to run for 7 hours 30 minutes (270
00 sec) and then heated to 155 ° C. to remove excess phenol. Resin distillation at 225 ° C, <2
Finished at mmHg (<0.3 Kpa). The results are shown in Table 1.

Example 18 (Production of epoxy resin
Concrete) stirrer, a condenser, a nitrogen blowing port, to a reactor equipped with a temperature bath and dropping funnel DOO was One attached in Example 2 phenol resin 878.5g (3.5 eq), propylene glycol methyl ether 880 g, 50% 3.0 g of NaOH,
17 g of water and 1618.7 g of epichlorohydrin
(17.5 mol) was charged. The solution was heated to 75 ° C. 700 g (3.5 mol) of 20% NaOH was added dropwise over 1 hour and 12 minutes (4320 sec). The reaction mass was held at 75 ° C. for 55 minutes (3300 seconds). The resin was transferred to a separatory funnel and separated into a brighton layer and a resin layer. The brine layer was removed, the resin solution was returned and heated to 75 ° C. 175 g of 20% NaOH (0.875 mol)
Was added over 27 minutes (1620 sec) and then held for another hour (3600 sec). Transfer the resin to a separatory funnel,
The brine layer was removed, washed with water, and the aqueous layer was removed. The resin solution was returned to the reactor again, and epichlorohydrin and propylene glycol methyl ether were removed by vacuum distillation. Distillation of resin is performed at 150 ℃, 2mmHg (0.3Kp
It ended in a). The resulting resin had an epoxy equivalent weight of 367 and was a semi-solid at room temperature.

Examples 19 to 32 (epoxy resin
Production of fats) Table 2 shows the results of epoxy resins prepared by using different phenolic resins. The manufacturing method was substantially the same as in Example 18. The resins prepared in Examples 18-32 were used with 0.87 mol of Nadic Methylanhydride (maleic anhydride adduct of methylcyclopentadiene) per epoxy equivalent and 1.5 wt% dimethylamine per epoxy resin pace. , The following cure was done. The physical properties are shown in Table 3. 90 ° C for 2 hours (7200sec) 165 ° C for 4 hours (14400sec) 200 ° C for 16 hours (57600sec)

The shrinkability of Examples 19, 20 and 23 was 2
Compared with that of some common epoxy resins. Typical resin (CR) 1 has an average epoxy equivalent (EEW) of 1
Phenol with an average epoxy functionality of 3.8 at 78
Formaldehyde epoxy novolac resin. General Resin 2 is a diglycidyl ether of Pisphenol A with an average EEW of 190. The resin was prepared by using 0.87 mol of Nadic methyl anhydride (maleic anhydride adduct of methylcyclopentadiene) per oxirane equivalent and 1.5 wt% of benzyldimethylamine based on the epoxy resin, and the following cure was used. did. 90 ° C. for 2 hours (7200 sec) 165 ° C. for 4 hours (14400 sec) 200 ° C. for 16 hours (57600 sec) 10 ″ × 1 ″ (25.4 cm × 2.54 cm) V-shaped mold linear shrinkage The latter was measured by measuring the length. The results are shown below. % Of shrinkage in resin cure CR1 0.98 CR2 0.99 Example 19 0.70 〃 20 0.75 〃 23 0.49 The temperature stability of the epoxy resins prepared in Examples 19 and 10 is as follows. Was used to compare with CR1. Using the same formulation and cure as described for shrinkage measurements, thickness 1/3 "(0.3175c
I made a casting from the transparent m). 1 "x 3"
(2.54 cm x 7.62 cm) sample at 260 ° C
The following results were obtained. These show excellent temperature stability as compared with known epoxides having good temperature stability.

The chemical resistance of the epoxy resins of Examples 19 and 20 was 1 ″ × 3 ″ (2.54 cm × 7.62 cm).
Of the sample was exposed to various solvents at 23 ° C. and compared with that of CR1. The weight change after each time exposure was recorded. The castings were made with the same prescription and cure schedule used for the shrinkage measurement. The results are shown in Table 4.

Example 33 (of solid epoxy resin
Manufacturing) 5 liters with stirrer, condenser and temperature controller 1 liter
A glass reactor was charged with 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 heating to 90 ° C., 0.07 part of an ethyltriphenylphosphonium acetate / acetic acid complex catalyst solution (70% methanol solution) was added. Then, after raising the temperature to 175 ° C., the temperature was maintained for 1 hour (3600 sec). The properties of the produced solid epoxy resin are shown below. EEW 768 Viscosity 6800cps 175 ° C (6.8Pa ・
s) Softening point 137.7 ° C

Example 34 (of solid epoxy resin
Manufacture) In a reaction vessel similar to Example 33, average epoxy equivalent 1
75 parts of diglycidyl ether of bisphenol A of 79 (0.42 epoxy equivalents) and 57.4 parts of a phenolic composition prepared as in Example 17 above (0.2
7 phenol equivalent) was charged. After heating to 90 ° C., 0.08 part of an ethyltriphenylphosphonium acetate / acetic acid complex catalyst solution (70% methanol solution) was added. After heating to 175 ° C., the temperature was maintained for 1 hour and 15 minutes (4500 seconds). The properties of the produced solid epoxy resin are shown below. EEW 778 Viscosity 7200 cps, 175 ° C (7.2 Pa ·
s) Softening point 127 ° C

Front Page Continuation (72) Inventor Nader Hoff, Brian A. Texas Texas 77566, Lake Jackson, Garland 415, Espayty 337

Claims (10)

[Claims] 1. Dehydrohalogenation of the reaction product of (a) an epoxyalkyl halide with (b) a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule. Components (a) and (b) are used in an amount such that the ratio of epoxy groups to phenolic hydroxyl groups is from 1.5: 1 to 20: 1, and component (b) is 1 per molecule. A composition having more than 1 phenolic hydroxyl group and more than 1 aromatic ring and being substantially free of ether groups, the composition comprising: (A) at least one aromatic hydroxy group and 1 At least one aromatic compound having at least one ortho or para position with respect to a hydroxyl group containing 2 to 2 aromatic rings and available for ring alkylation, and (B) at least one Acid-catalyzed reaction with unsaturated hydrocarbons of components (A) and (B) in a molar ratio of component (A) to component (B) of 1.8: 1 to 30: 1. Mono catalyst used in an amount, and the catalyst is used in an amount of 0.01 to 5% by weight, based on the weight of component (A), and component (B) is (1) a monomer having 4 to 6 carbon atoms. Unsaturated or diunsaturated hydrocarbons or mixtures thereof; (2) unsaturated hydrocarbons containing an average of 6 to 55 carbon atoms per molecule; and containing up to 94% by weight of dicyclopentadiene; (3) ) Diene oligomers and / or cooligomers of diene having from 4 to 18 carbon atoms and containing at least 6% by weight of dienes other than dicyclopentadiene; and (4) selected from mixtures thereof. It is characterized by Method for producing an epoxy resin composition. 2. The component (B) is dicyclopentadiene 2
0-94% by weight, dicyclopentadiene and C _4-6
1-30% by weight of dimers other than hydrocarbon co-dimers,
A composition comprising 0 to 10% by weight of an oligomer of a C _{4 to} C ₆ diene, and the C _{4 to} C ₆ alkane, alkene, if any, and the balance to provide 100% by weight of the diene. The method according to claim 1. 3. The component (B) is dicyclopentadiene 70.
To 94% by weight, dicyclopentadiene and _C 4 -C ₆ dimer 6-30% by weight of other co-dimer of hydrocarbons hydrogen, C
₄ -C ₆ oligomer 0-7 wt% of a diene, and it is dicyclopentadiene concentrate containing the remainder to provide alkane C ₄ -C _6, a 100 wt% alkenes and dienes as there if The method according to claim 2, characterized in that 4. The component (B) is dicyclopentadiene 20.
˜70 wt%, dicyclopentadiene and dimer other than C ₆ hydrocarbon codimer 1-10 wt%, C ₄ -C
Oligomer of ₆ diene 0-10% by weight, and C ₄ -C
Process according to claim 2, characterized in that it is a crude dicyclopentadiene stream containing the alkane of ₆ , the alkene and the balance to provide 100% by weight of the diene. 5. The component (B) comprises 30 to 70% by weight of piperylene or isoprene and C _{9 to} C of C _{4 to} C ₆ diene.
A crude piperene or crude isoprene stream containing 0 to 10% by weight of ₁₂ dimers or codimers, and the balance to provide 100% by weight of C _{4 to} C ₆ alkanes, alkenes and dienes. The method according to claim 1. 6. The component (B) is piperylene dimer 90.
~ 100 wt%, high molecular weight oligomers of piperylene 0 ~
The process according to claim 1, which is an unsaturated hydrocarbon composition containing 10% by weight and 0 to 4% by weight of piperylene. 7. Component (B) contains an unsaturated hydrocarbon produced by the oligomerization of a dicyclopentadiene concentrate, the oligomerization product of which is on average 1 per molecule.
Process according to claim 1, characterized in that it contains from 2 to 55 carbon atoms. 8. In the presence of an effective amount of a suitable catalyst,
(I) reacting at least one epoxy resin having an average of more than 1,2-epoxy groups per molecule with (II) at least one substance having an average of more than 1 phenolic hydroxyl group per molecule. Including the component (I
I) is a phenolic hydroxyl group-containing composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule and substantially free of ether groups, the composition comprising: ) A hydroxyl group containing at least one aromatic hydroxy group and one or two aromatic rings and having at least one ortho or para position, which is available for ring alkylation. Made from an acid-catalyzed reaction of an aromatic compound with (B) at least one unsaturated hydrocarbon, wherein components (A) and (B) are in a molar ratio of component (A) to component (B). Is used in an amount of 1.8: 1 to 30: 1, and the catalyst is used in an amount of 0.01 to 5 wt% based on the weight of component (A), and component (B) is ) Mono-containing 4 to 6 carbon atoms Saturated or diunsaturated hydrocarbons or mixtures thereof; (2) unsaturated hydrocarbons containing an average of 6 to 55 carbon atoms per molecule; and containing up to 94% by weight of dicyclopentadiene; (3) An oligomer and / or cooligomer of a hydrocarbon diene in which the diene has from 4 to 18 carbon atoms and containing at least 6% by weight of a diene other than dicyclopentadiene; and (4) a mixture thereof. A method for producing a solid composition comprising: 9. Component (I) is the reaction product of (a) an epoxyalkyl halide and (b) a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule. Made from the dehydrohalogenation of the product, components (a) and (b) are used in an amount such that the ratio of epoxy groups to phenolic hydroxyl groups is from 1.5: 1 to 20: 1, and component (b) ) Is a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule and substantially free of ether groups, the composition comprising (A) at least one At least one aromatic compound having at least one ortho or para position with respect to a hydroxyl group containing an aromatic hydroxy group and one or two aromatic rings and available for ring alkylation; (B) Made from an acid-catalyzed reaction with at least one unsaturated hydrocarbon, wherein components (A) and (B) have a molar ratio of component (A) to component (B) of 1.8: 1 to 30. 1) and the catalyst is used in an amount of 0.01 to 5% by weight, based on the weight of component (A), and component (B) is (1) 4 to 6 carbon atoms. An unsaturated hydrocarbon containing an average of 6 to 55 carbon atoms per molecule; and containing 94% by weight or less of dicyclopentadiene. (3) oligomers and / or cooligomers of hydrocarbon dienes in which the diene has from 4 to 18 carbon atoms and containing at least 6% by weight of dienes other than dicyclopentadiene; and (4) those Choose from a mixture Section 8 of the method claims, characterized in Rukoto. 10. Component (I) is the reaction product of (a) an epoxyalkyl halide and (b) a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule. Made from the dehydrohalogenation of the product, components (a) and (b) are used in an amount such that the ratio of epoxy groups to phenolic hydroxyl groups is from 1.5: 1 to 20: 1, and component (b) ) Is a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule and substantially free of ether groups, the composition comprising (A) at least one At least one aromatic compound having at least one ortho or para position with respect to a hydroxyl group containing an aromatic hydroxy group and one or two aromatic rings and available for ring alkylation; (B ) Made from an acid-catalyzed reaction with at least one unsaturated hydrocarbon, in which the components (A) and (B) have a molar ratio of component (A) to component (B) of from 1.8: 1 to 30: 1, and the catalyst is used in an amount of 0.01 to 5% by weight, based on the weight of component (A), component (B) being (1) 4 to 6 carbons. Unsaturated carbons having an average of 6 to 55 carbon atoms per molecule; and 94% by weight or less of dicyclopentadiene. Hydrogen; (3) oligomers and / or cooligomers of hydrocarbon dienes in which the diene has from 4 to 18 carbon atoms and containing at least 6% by weight of dienes other than dicyclopentadiene; and (4) them. Select from a mixture of Component (II) is a composition having more than one phenolic hydroxyl group and more than one aromatic ring per molecule and being substantially free of ether groups, the composition comprising: ) A hydroxyl group containing at least one aromatic hydroxy group and one or two aromatic rings and having at least one ortho or para position, which is available for ring alkylation. Made from an acid-catalyzed reaction of an aromatic compound with (B) at least one unsaturated hydrocarbon, wherein components (A) and (B) are in a molar ratio of component (A) to component (B). Is used in an amount of 1.8: 1 to 30: 1, and the catalyst is used in an amount of 0.01 to 5 wt% based on the weight of component (A), and component (B) is ) Monounsaturated compounds having 4 to 6 carbon atoms Or a diunsaturated hydrocarbon or a mixture thereof; (2) an unsaturated hydrocarbon containing an average of 6 to 55 carbon atoms per molecule; and containing 94% by weight or less of dicyclopentadiene; (3) An oligomer and / or cooligomer of a hydrocarbon diene in which the diene has from 4 to 18 carbon atoms and containing at least 6% by weight of a diene other than dicyclopentadiene; and (4) a mixture thereof. The method of claim 8 wherein: