CN107540816B - Preparation and application of copolymer epoxy resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol - Google Patents
Preparation and application of copolymer epoxy resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol Download PDFInfo
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Abstract
The invention provides a novel dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer epoxy resin (the molecular structure is shown as formula 1) with excellent heat resistance, low dielectric constant Dk and low loss factor Df, which is prepared by two steps: reacting (a1) dicyclopentadiene-phenol resin (formula 2) with (a2)2, 6-dimethylphenol in the presence of an acidic catalyst by (a3) aldehyde compounds to form a copolymer phenol resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol, step two: preparing copolymer epoxy resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol by using the copolymer phenolic resin and excessive epoxy chloropropane under the condition of NaOH, substituting the copolymer epoxy resin into a glass fiber laminated board formula composition, and after water absorption in a pressure cooker PCT for 2hr, dip-soldering tin at 288 ℃ for heat resistance of no-explosion board for more than 10 minutes. Wherein x is an integer of 0to 5 and y is an integer of 0to 5; r represents: hydrogen, C1-C10 alkyl, phenyl, hydroxyphenyl, and the like.
Description
Technical Field
The invention relates to dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer epoxy resin and a preparation method thereof, and the dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer epoxy resin is substituted into a glass fiber laminated board formula composition, and a hardened substance of the dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer epoxy resin has good heat resistance, high glass transition temperature Tg, low dielectric constant Dk and low loss factor Df, and is suitable for high-performance printed circuit boards, semiconductor packaging materials and other insulating materials of electronic components with high reliability requirements.
Background
Patent No. TW216439 describes that Dicyclopentadiene-phenol epoxy resin (Dicyclopentadiene-phenol) is a special skeleton-structured epoxy resin, which contains alicyclic six-membered rings, five-membered rings and aromatic benzene rings, has Dicyclopentadiene structure with excellent heat resistance and low polarity, has low water absorption with the hardened product of the hardening agent, excellent electrical properties (low dielectric constant Dk and low dissipation factor Df), and the structure of Dicyclopentadiene has the function of reducing the internal stress of the hardened product, and excellent mechanical properties, so that Dicyclopentadiene-phenol epoxy resin has been used in the fields of glass fiber laminates and printed circuit boards, and the phenolic hydroxyl group (phenolic OH group) of Dicyclopentadiene-phenol resin is further reacted and extended to synthesize Benzoxazine resin (benzoxazinone), active ester resin (active ester), high performance resin with a phenyl structure, and the like, which have excellent electrical properties, lower dielectric constant and loss factor, and can meet the trend requirements of high-frequency and high-speed electronic products. However, we have studied the electrical properties of dicyclopentadiene-phenol epoxy resins for a long time, which have a better effect of reducing the dielectric constant Dk and a smaller effect of reducing the loss factor Df.
Patent TW201038151 discloses that 2, 6-dimethylphenol reacts with aldehydes to synthesize bifunctional 2, 6-dimethylphenol aldehyde resin under an acidic catalyst, the bifunctional 2, 6-dimethylphenol aldehyde resin and Epichlorohydrin (ECH) synthesize bifunctional 2, 6-dimethylphenol aldehyde epoxy resin in the presence of sodium hydroxide NaOH, and the bifunctional 2, 6-dimethylphenol aldehyde resin has a highly symmetric chemical structure and a low molecular dipole moment, so that the dielectric constant (Dk) and the loss factor (Df) can be effectively reduced, the bifunctional 2, 6-dimethylphenol is also a raw material for synthesizing a low dielectric constant (Dk) and a low loss factor (Df) material, namely, polyphenylene ether resin (PPE), which has a very low loss factor (Df) characteristic, and the loss factor is smaller, which means that the signal transmission loss is smaller, while the bifunctional 2 synthesized in the aforementioned patent TW201038151, although the 6-dimethylphenyl novolac epoxy resin can effectively reduce the dielectric constant (Dk) and the loss factor (Df), the bifunctional 2, 6-dimethylphenyl novolac epoxy resin has a lower crosslinking density, a lower glass transition temperature Tg and poorer heat resistance.
In order to meet the requirement of high-speed transmission of electronic communication products, the trend of high-speed and high-frequency signals of electronic equipment is always developing, and the trend of light, thin, short and small electronic components is also toward providing a resin which can combine low dielectric constant (Dk), low loss factor (Df) and requirements of extremely high heat resistance and high glass transition temperature (Tg), which is a desired issue in the printed circuit board industry.
Disclosure of Invention
Accordingly, the present invention has been made to solve the above problems, and an object of the present invention is to provide a dicyclopentadiene-phenol resin and 2, 6-dimethylphenol copolymer epoxy resin which has not only both of the excellent electrical properties (low dielectric constant Dk, low dissipation factor Df) of the dicyclopentadiene-phenol epoxy resin and the 2, 6-dimethylphenol epoxy resin but also better heat resistance than the above resins, and which has both of the excellent electrical properties of the dicyclopentadiene-phenol epoxy resin and the 2, 6-dimethylphenol epoxy resin, particularly the low dissipation factor Df of the 2, 6-dimethylphenol epoxy resin, and which has both of the excellent electrical properties of the dicyclopentadiene-phenol epoxy resin and the 2, 6-dimethylphenol copolymer epoxy resin, the copolymer is prepared by reacting and adding dicyclopentadiene-phenol resin and 2, 6-dimethylphenol phenol formaldehyde resin together and reacting with epichlorohydrin to form dicyclopentadiene-phenol resin and 2, 6-dimethylphenol phenol formaldehyde resin copolymer epoxy resin, and compared with dicyclopentadiene-phenol epoxy resin and 2, 6-dimethylphenol phenol formaldehyde resin, the copolymer epoxy resin has a reaction epoxy group with a higher functional group number, has higher hardening and bridging density and better heat resistance and mechanical property, and the novel epoxy resin is substituted into a formula of a glass fiber laminated plate, and a hardened product of the novel epoxy resin also has a low dielectric constant (Dk), a low loss factor (Df), excellent mechanical property and high glass transition temperature Tg, and simultaneously has excellent heat resistance, so that the copolymer is suitable for being applied to copper foil glass fiber laminated plates, printed circuit boards and the like, The semiconductor packaging material meets the requirements of high-speed transmission of electronic communication products and high-speed and high-frequency signals of electronic equipment.
The method for preparing the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol of the invention is to perform condensation reaction on dicyclopentadiene-phenol resin with low dielectric constant (Dk) and low loss factor (Df) and 2, 6-dimethylphenol with an aldehyde compound in the presence of an acid catalyst to obtain copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol with higher average functional group number (6-12), synthesize the copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol and excessive epichlorohydrin into copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol under the condition of NaOH, synthesize the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol, the cured epoxy resin obtained by the method is low in dielectric constant (Dk), low in dissipation factor (Df) and excellent in heat resistance and high Tg together with common epoxy resin hardeners such as dicyandiamide, phenolic resin PN hardener, styrene-maleic anhydride copolymer SMA, Benzoxazine resin (Benzoxazine), polyphenylene ether resin (PPE) and active ester resin (active ester).
The invention relates to a novel dicyclopentadiene-phenol resin and 2, 6-dimethylphenol copolymer epoxy resin, which has a molecular structure shown in the following structural formula 1:
formula 1
Wherein X is an integer of 0to 5 and Y is an integer of 0to 5;
r represents: hydrogen, C1-C10 alkyl, phenyl, hydroxyphenyl, and the like.
The preparation of the novel dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer epoxy resin comprises two steps, namely: reacting (a1) dicyclopentadiene-phenol resin (shown as the following formula 2) with (a2)2, 6-dimethylphenol in the presence of an acidic catalyst by (a3) aldehyde compounds to form a copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol;
formula 2:
x is an integer of 0to 5
The reaction is carried out in a ratio of 1 to 2.5 moles of (a2)2, 6-dimethylphenol to 1 mole of a phenolic hydroxyl group (phenolic OH) in (a1) dicyclopentadiene-phenol resin and 0.8 to 1.5 moles of (a3) aldehyde compound. Step two: the copolymer of dicyclopentadiene-phenol and 2, 6-dimethylphenol and excessive Epichlorohydrin are used for preparing copolymer epoxy resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol under the condition of NaOH, the equivalent ratio of the copolymer of dicyclopentadiene-phenol and 2, 6-dimethylphenol to Epichlorohydrin (ECH) is 1: 1-8, and the equivalent ratio of the copolymer of dicyclopentadiene-phenol and 2, 6-dimethylphenol to alkali NaOH is 1: 0.95-1.1.
The dicyclopentadiene-phenol resin and 2, 6-dimethylphenol copolymer epoxy resin of the invention has the characteristic effect that dicyclopentadiene-phenol resin and 2, 6-dimethylphenol are combined by two excellent electric (low dielectric constant Dk and low loss factor Df) resins for reaction and then are epoxidized, so that the dicyclopentadiene-phenol epoxy resin has the excellent low dielectric constant Dk and low water absorption characteristic, and the 2, 6-dimethylphenol epoxy resin has the excellent low dielectric constant Dk and low loss factor Df, so that the novel dicyclopentadiene-phenol resin and 2, 6-dimethylphenol copolymer epoxy resin has the electric (low dielectric constant Dk and low loss factor Df) better than dicyclopentadiene-phenol epoxy resin, and the synthesis preparation method is that dicyclopentadiene-phenol resin and 2, 6-dimethylphenol are subjected to condensation dehydration reaction with aldehyde compounds under an acid catalyst to ensure that the two resin phases are in phase Bonding, namely combining a plurality of reaction points in the dicyclopentadiene-phenol resin with the 2, 6-dimethylphenol by utilizing aldehyde compound bridging (the following reaction formula),
n, x, y is an integer of 0to 5
The number f of phenolic hydroxyl (phenolic OH) functional groups on the copolymer structure is equal to the number (n +2) of phenolic hydroxyl groups of the dicyclopentadiene-phenol resin plus the number x + y +2 of 2, 6-dimethylphenol bonded to the dicyclopentadiene-phenol resin, however, x + y is equal to n, i.e., f is equal to 2n +4, the copolymer has a higher number of phenolic hydroxyl groups than the dicyclopentadiene-phenol resin or the 2, 6-dimethylphenol phenol resin, the number of functional groups of the phenolic hydroxyl groups is proportional to the number of equivalents of aldehyde compounds to be synthesized, the number of equivalents of aldehyde compounds is larger, meaning that the more bridge bonds are present, the higher the number of phenolic hydroxyl functional groups of the dicyclopentadiene-phenol resin and the 2, 6-dimethylphenol copolymer is, the number average molecular weight Mn and the phenolic hydroxyl equivalent weight are 150g/eq by GPC analysis of a gel chromatograph, according to the theoretical formula: the functional group number is Mn/phenolic hydroxyl equivalent, the average value of the calculated theoretical functional group number is 6-10, the phenolic hydroxyl of the copolymer of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol is epoxidized to form the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol, the copolymer epoxy resin has the characteristics of high functional group, the heat resistance after hardening is good, the glass transition temperature Tg is high, and the dicyclopentadiene-phenol resin and 2, 6-dimethylphenol copolymer epoxy resin with good expected effects, such as Low Dk and Df, high heat resistance and high Tg, is obtained.
The invention further relates to a preparation method of copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol, which comprises two steps: adding an acidic catalyst into 1 mol of phenolic hydroxyl (OH) in dicyclopentadiene-phenol resin (a1) and 1-2.5 mol of 2, 6-dimethylphenol (a2), dissolving 0.8-1.5 mol of aldehyde compound in water, dropwise adding the aldehyde compound into the reaction mixture, reacting at the temperature of 95-115 ℃, dropwise adding aldehyde compound aqueous solution for reacting for 1-6 hours, wherein the acidic catalyst is usually methanesulfonic acid (MSA), p-toluenesulfonic acid (PTSA), oxalic acid, hydrochloric acid and the like, the dosage of the acidic catalyst is 0.5-5% relative to the dosage of the dicyclopentadiene-phenol resin, and the aldehyde compound is usually formaldehyde, acetaldehyde, glyoxal, benzaldehyde and the like, neutralizing after the reaction, removing 2, 6-dimethylphenol, washing with water, and removing a solvent to obtain the dicyclopentadiene-phenol resin and 2, 6-dimethylphenol copolymer phenolic resin. Step two: preparing copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol from the copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol and excessive Epichlorohydrin and NaOH under a common epoxidation condition, wherein the equivalent ratio of the copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol to Epichlorohydrin (ECH) is 1: 1-8, the equivalent ratio of the copolymer of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol to alkali NaOH is 1: 0.95-1.1, the main reaction temperature of epoxidation is 50-100 ℃, and then carrying out epoxy chloropropane removal, refining reaction, desalting and neutralization, washing with water, filtering the solution, and removing the solvent to obtain the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol.
The invention further discloses an epoxy resin varnish composition for the glass fiber laminated plate, which comprises the following components in percentage by weight: the component (A) is a copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol, and the usage amount accounts for 30-80% of the total resin (the total resin is equal to the sum of the component (A) and the component (IV)). The component (di) multifunctional or bifunctional or modified epoxy resin, which is used in an amount of 0-25% based on the total resin, is selected from the group consisting of o-cresol novolac epoxy resin, benzaldehyde-phenol multifunctional epoxy resin, dicyclopentadiene-phenol epoxy resin, bisphenol A novolac epoxy resin, tetraphenylolethane novolac epoxy resin, tris (hydroxyphenyl) methane novolac epoxy resin, phosphorous epoxy resin, 2, 6-dimethylphenol novolac epoxy resin, brominated epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol A epoxy resin, and epoxy-isocyanate copolymer. The curing agent (III) accounts for 15-60% of the total resin, and is selected from phenolic resin, bisphenol A type phenolic resin, Dicyclopentadiene-phenol resin, benzaldehyde-phenol resin, melamine-phenol phenolic resin (melamine-phenolic), active ester curing agent, styrene-maleic anhydride copolymer (SMA), bisphenol A type Benzoxazine (BPABenzoxazine), bisphenol F type Benzoxazine (BPF Benzoxazine), Dicyclopentadiene-phenol Benzoxazine (Dicyclopentadiene-phenol), and polyphenylene ether (PPE). Or any two or more (inclusive) of the aforementioned hardening agents. The component (IV) is a flame retardant, the usage amount accounts for 10-40% of the total resin, and the flame retardant comprises a reaction type flame retardant and an addition type flame retardant, and is selected from a phosphorus-containing bisphenol A type phenolic hardener (the phosphorus content is 5-10%), hexaphenoxycyclotriphosphazene (the phosphorus content is 13.4%, the nitrogen content is 8%), and tetrabromobisphenol A (the bromine content is 58.5%). The filler (V) is selected from silicon dioxide and aluminum hydroxide, and accounts for 0-45% of the total varnish composition (calculated by solid state, the solid varnish composition is equal to the sum of the first component and the fifth component). The component (VI) is a hardening accelerator, which is used in an amount of 0.01 to 0.2% (relative to the epoxy resin and the hardening agent, i.e., the sum of the component (I) to the component (III)), and is selected from the group consisting of dimethylimidazole, diphenylimidazole, diethyltetramethylimidazole and benzyldimethylamine. The component (VII) solvent, the amount of which is 50-70% of the solid content of the varnish composition, is selected from acetone, butanone, cyclohexanone, dimethoxyethanol (MCS), propylene glycol methyl ether (PM) and toluene.
The epoxy resin copolymer of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol of the present invention and the cured product obtained by heat-curing the varnish composition thereof can be used in various applications including insulating materials for high-reliability motor/electronic components such as PCB printed circuit boards, EMC semiconductor packages, and the like, and coatings and adhesives requiring excellent electrical characteristics and thermal stability.
The invention has the following effects: according to the preparation method and the application of the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol provided by the invention, a cured product obtained by a varnish composition through a thermal curing reaction shows excellent heat resistance, low dielectric constant, low loss factor, high Tg and the like, and accords with the high-speed and high-frequency development trend of the future electronic industry.
Detailed Description
The present invention will be more clearly understood from the following detailed description.
The most remarkable characteristic of the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol of the invention is that the dicyclopentadiene-phenol epoxy resin and the 2, 6-dimethylphenol novolac epoxy resin are combined in a reactive grafting way, so that the copolymer epoxy resin of the invention has better electrical property (low dielectric constant Dk, low loss factor Df) and heat resistance and Tg characteristic than the two resins, the dicyclopentadiene-phenol resin and the 2, 6-dimethylphenol novolac resin are combined in a reactive grafting way by aldehyde compounds under an acid catalyst and then are subjected to an epoxidation reaction with epichlorohydrin to form the epoxy resin, and as the reactive grafting combination is adopted, the epoxy group number is more, the hardening and bridging density is higher, so that the electrical property (low dielectric constant Dk, low loss factor Df) and the heat resistance are caused, the Tg characteristics are better than the two aforementioned resins.
Specifically, the method for preparing the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol of the present invention comprises two steps, step one (synthesis of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol copolymer phenolic resin): adding 1 mol of phenolic hydroxyl (phenolic OH) in dicyclopentadiene-phenol resin (a1) and 1-2.5 mol of 2, 6-dimethylphenol (a2) into a medium-boiling low-volume water solvent (boiling point >110 ℃), adding an acidic catalyst, heating to 95-115 ℃, dissolving 0.8-1.5 mol of aldehyde compound in water to prepare a 20-50% aqueous solution of aldehyde compound (if the aldehyde compound is in a liquid state, the aqueous solution does not need to be prepared), dropwise adding the aqueous solution of aldehyde compound into the reaction mixture at the dropwise adding reaction temperature of 95-115 ℃, dropwise adding the aqueous solution of aldehyde compound for 1-6 hours, wherein the acidic catalyst is usually Methyl Sulfonic Acid (MSA), p-toluenesulfonic acid (PTSA), oxalic acid, hydrochloric acid and the like, the amount of the acidic catalyst is 0.5-5% relative to the amount of dicyclopentadiene-phenol resin, the aldehyde compound is usually formaldehyde, acetaldehyde, glyoxal, benzaldehyde and the like, and the water needs to be removed in the reaction process, the hydroformylation product can be reacted completely, and the solvent is added for azeotropic water to take out water and separate phase with water to remove water phase, and is selected from medium boiling point low water content solvent such as methyl isobutyl ketone (MIBK), toluene, etc. The dosage of the solvent is 5-20% relative to the dosage of the dicyclopentadiene-phenol resin. After the dropwise addition reaction is finished, the reaction is carried out for 30 minutes to 2 hours. After the reaction, the acid catalyst is neutralized by alkali, and the alkali is not limited to alkali commonly used in industry such as sodium hydroxide, potassium hydroxide, amines and the like. And (3) neutralizing until the pH value is 6-7, heating to remove the solvent and the 2, 6-dimethylphenol, wherein the temperature is 175-185 ℃, and after the temperature reaches 175-185 ℃, slowly reducing the vacuum degree to avoid bumping, and finally, the vacuum degree is less than 5 torr. Maintaining the temperature at 175-185 ℃ for 1 hour under the vacuum degree of <5 torr. Adding solvent such as methyl isobutyl ketone (MIBK), toluene, etc. to dissolve, adding water to perform desalting, water washing, filtering, and solvent removing to obtain copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol.
Step two (synthesis of copolymer epoxy resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol): and (3) preparing the copolymer of dicyclopentadiene-phenol and 2, 6-dimethylphenol from the copolymer of dicyclopentadiene-phenol and 2, 6-dimethylphenol obtained in the step one with excessive epichlorohydrin and sodium hydroxide (NaOH) under a common epoxidation condition, and performing steps (1) to (5). (1) Pre-reaction: the equivalent ratio of copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol to Epichlorohydrin (ECH) is 1: 1-8, 10-40% of cosolvent relative to the amount of copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol is added, the cosolvent is selected from propylene glycol monomethyl ether (PM) or alcohols, 49.5% of sodium hydroxide (NaOH) is added, the equivalent ratio of copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol to alkali NaOH is 1: 0.1-0.2, the pre-reaction temperature is 50-100 ℃, and the pre-reaction time is 2-4 hours. (2) Main reaction: dripping 1 equivalent of copolymer phenolic resin of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol in a reactant by 0.77-0.97 equivalent ratio of 49.5% NaOH at a reaction temperature of 60-65 ℃ under a vacuum degree of 160-190 torr, and dripping for 2-5 hours in a main reaction process, wherein in the main reaction process, water in a system is brought out by azeotropic boiling of ECH and water, and is refluxed into the system through a lower layer of ECH in a phase separation barrel, and an upper layer of water is discharged. (3) Removing epoxy chloropropane: the excess epichlorohydrin ECH was removed at a temperature of 160 ℃ and a vacuum of <5 torr. (4) And (3) refining reaction: adding a solvent to prepare a 30-50% solid resin solution, adding 20% sodium hydroxide NaOH to carry out a refining reaction, wherein the addition amount of the 20% sodium hydroxide NaOH is divided by the measured hydrolysable chlorine value by 35.5 × 40 × the refining coefficient by 1.5 × the weight of the resin by 0.2, the refining temperature is 70-90 ℃, the refining reaction time is 1-3 hours, adding water to carry out desalination and liquid separation after the reaction is finished, neutralizing, washing and liquid separation, filtering the resin solution, and removing the solvent to obtain the dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer epoxy resin.
More specifically, the method for preparing the dicyclopentadiene-phenol/2, 6-dimethylphenol copolymer epoxy resin of the present invention comprises the first to second steps of adding a medium-boiling low-volume water solvent (boiling point >110 ℃) to 1 mol of phenolic hydroxyl group (phenolic OH) and 1 to 2.5 mol of (a2)2, 6-dimethylphenol in (a1) dicyclopentadiene-phenol resin, adding an acidic catalyst, heating to 95 to 115 ℃, dissolving 0.8 to 1.5 mol of a aldehyde compound in water to prepare a 20 to 50% water solution of the aldehyde compound (if the aldehyde compound is in a liquid state, it is not necessary to prepare an aqueous solution), dropwise adding the aqueous solution into the reaction mixture, removing water during the reaction to allow the reaction to reach a high conversion rate and a high reaction rate, taking out water by the medium-boiling low-volume water solvent, separating the aqueous layer into a phase separation tank, removing the lower layer, the upper layer solvent flows back to the reaction system, and the aldehyde compound aqueous solution is dropwise added, so that the aldehyde compound reaction efficiency is better, and the reaction is more complete. There are two possibilities for this step of reaction, one being dicyclopentadiene-phenol resin by reaction of the aldehyde not only with itself dicyclopentadiene-phenol but also with 2, 6-dimethylphenol, and two being 2, 6-dimethylphenol by reaction of the aldehyde with itself 2, 6-dimethylphenol. The weight average molecular weight of the obtained product is in positive correlation with the feeding amount of aldehyde compound, the feeding equivalent of aldehyde compound does not exceed the sum of the equivalent amounts of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol, and the feeding equivalent of aldehyde compound is preferably in the range of 0.8 to 1.2.
Step two: and (2) synthesizing the copolymer phenolic resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol obtained in the step one into copolymer epoxy resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol under common epoxidation conditions, namely, carrying out epoxidation synthesis on the copolymer phenolic resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol by using excessive epoxy chloropropane in the presence of sodium hydroxide.
Preferred embodiments of the present invention will be described in detail with reference to the following examples.
Synthesis example a: (Synthesis of copolymer of Dicyclopentadiene-phenol and 2, 6-dimethylphenol epoxy resin A)
170g (1 mol of phenolic hydroxyl) of dicyclopentadiene-phenol resin (product name NPEH-772L of south Asia plastics, softening point 85 ℃), 170g of 2, 6-dimethylphenol, 30g of methyl isobutyl ketone (MIBK) as a solvent and 1.7g of methanesulfonic acid MSA as a catalyst are mixed and heated to 107 ℃, 130g of 23% formaldehyde solution is dropwise added at 107 ℃ for reaction for 3.5 hours and is continuously aged at 107 ℃ for reaction for 1Hr, after the reaction is finished, 0.8g of 49.5% NaOH aqueous solution is added to neutralize the mixture until the pH value is 6-7, the mixture is heated to 140 ℃ for dehydration, the temperature is raised to 185 ℃, and the vacuum degree is slowly reduced to 5 torr. The temperature and vacuum were maintained at 185 ℃ C.. times.5 torr for 1 hour. Cooling, breaking vacuum, adding 550g of methyl isobutyl ketone solvent, stirring at 80 ℃ for 60 minutes to dissolve, adding 50g of water, standing at 80 ℃ for layering, draining the lower salt water layer, adding 50g of water for washing, standing at 80 ℃ for layering, draining the lower salt water layer, and repeating the washing step for 1 time. After the solution is filtered, the solution is dehydrated at 120 ℃, the temperature is continuously raised to 180 ℃, the vacuum degree is reduced to 5torr, and the solvent methyl isobutyl ketone (MIBK) is removed, so that the copolymer phenolic resin A of dicyclopentadiene-phenol and 2, 6-dimethylphenol is obtained, the yield is 99.5 percent, and the quality condition is as follows: average molecular weight Mw2500, softening point 126 deg.C, phenolic hydroxyl equivalent 150 g/eq.
150g of dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer resin phenolic resin A, 555g of epoxy chloropropane and 166g of propylene glycol monomethyl ether PM are mixed, dissolved and heated to 60 ℃, 12.1g of 49.5 percent sodium hydroxide NaOH is added for pre-reaction, and the pre-reaction time is 3 hours; then 66g of 49.5 percent sodium hydroxide is dripped into the mixed solution for main reaction, the main reaction temperature is 62 ℃, the vacuum degree is 180torr, the main reaction time is 4 hours, the main reaction is finished at 150 ℃ and 10torr, and dehydration and ECH removal are carried out after 1 hour of maintenance; adding 207g of solvent methyl isopropyl ketone, dissolving for 30 minutes at 80 ℃, adding 196g of pure water, stirring for 15 minutes at 80 ℃, standing for phase separation, and draining a lower salt water layer; the resin was analyzed for hydrolyzable chlorine value of 2500ppm, and purification reaction was conducted at 80 ℃ with the addition of 1.75g of 49.5% sodium hydroxide and 2g of pure water for 2 hours. Adding 276g of solvent MIBK, stirring for 15 minutes at 80 ℃ for standing and phase splitting, draining the lower water layer, adding 30g of pure water and 20g of 10% NaH2PO4, stirring for 15 minutes at 80 ℃, standing and phase splitting, analyzing the pH value to be 6-7, draining the lower water layer, adding 40g of pure water, stirring for 15 minutes at 80 ℃, standing and phase splitting, draining the lower water layer, heating to 117 ℃, performing circulation dehydration for 1 hour, filtering the solution, heating to 150 ℃, gradually reducing the vacuum degree to 5torr, and maintaining for 1 hour at 150 ℃ and 5torr to obtain the dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer epoxy resin A.
Quality condition: epoxy equivalent weight 228g/eq, hydrolyzable chlorine 240ppm, weight average molecular weight Mw 3500.
Synthesis example B: (Synthesis of copolymer of Dicyclopentadiene-phenol and 2, 6-dimethylphenol epoxy resin B)
180g (1 mol of phenolic hydroxyl) of dicyclopentadiene-phenol resin (product name NPEH-772H of south Asia plastics, softening point 110 ℃), 170g of 2, 6-dimethylphenol, 30g of methyl isobutyl ketone (MIBK) as a solvent and 1.7g of methanesulfonic acid MSA as a catalyst are mixed and heated to 107 ℃, 130g of 23% formaldehyde solution is dropwise added at 107 ℃ for reaction for 3.5 hours and is continuously aged at 107 ℃ for reaction for 1Hr, after the reaction is finished, 0.8g of 49.5% NaOH aqueous solution is added to neutralize the mixture until the pH value is 6-7, the mixture is heated to 140 ℃ for dehydration, the temperature is raised to 185 ℃, and the vacuum degree is slowly reduced to 5 torr. The temperature and vacuum were maintained at 185 ℃ C.. times.5 torr for 1 hour. Cooling, breaking vacuum, adding 550g of methyl isobutyl ketone solvent, stirring at 80 ℃ for 60 minutes to dissolve, adding 50g of water, standing at 80 ℃ for layering, draining the lower salt water layer, adding 50g of water for washing, standing at 80 ℃ for layering, draining the lower salt water layer, and repeating the washing step for 1 time. Filtering the solution, dehydrating at 120 ℃, continuously heating to 180 ℃, reducing the vacuum degree to 5torr, and removing a solvent methyl isobutyl ketone (MIBK) to obtain a dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer phenolic resin B with the yield of 99.5 percent and the quality condition: average molecular weight Mw2800, softening point 129 ℃, phenolic hydroxyl equivalent weight 154 g/eq.
Mixing and dissolving dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer resin B154 g, epichlorohydrin 555g and propylene glycol monomethyl ether PM 166g, heating to 60 ℃, adding 49.5 percent of sodium hydroxide NaOH 12.1g for pre-reaction, and pre-reacting for 3 hours; then 66g of 49.5 percent sodium hydroxide is dripped into the mixed solution for main reaction, the main reaction temperature is 62 ℃, the vacuum degree is 180torr, the main reaction time is 4 hours, the main reaction is finished at 150 ℃ and 10torr, and dehydration and ECH removal are carried out after 1 hour of maintenance; adding 207g of solvent methyl isopropyl ketone, dissolving for 30 minutes at 80 ℃, adding 196g of pure water, stirring for 15 minutes at 80 ℃, standing for phase separation, and draining a lower salt water layer; the resin was analyzed for hydrolyzable chlorine value of 2200ppm, and refining reaction was carried out at 80 ℃ with the addition of 49.5% sodium hydroxide 1.70g and 2g of pure water for 2 hours. Adding 276g of solvent MIBK, stirring for 15 minutes at 80 ℃ for standing and phase splitting, draining the lower water layer, adding 30g of pure water and 20g of 10% NaH2PO4, stirring for 15 minutes at 80 ℃, standing and phase splitting, analyzing the pH value to be 6-7, draining the lower water layer, adding 40g of pure water, stirring for 15 minutes at 80 ℃, standing and phase splitting, draining the lower water layer, heating to 117 ℃, performing circulation dehydration for 1 hour, filtering the solution, heating to 150 ℃, gradually reducing the vacuum degree to 5torr, and maintaining for 1 hour at 150 ℃ and 5torr to obtain the dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer epoxy resin B.
Quality condition: epoxy equivalent 232g/eq, hydrolyzable chlorine 210ppm, weight average molecular weight Mw 3800.
Examples 1-5 copper-clad plate formula physical properties are shown in Table I
Examples 1 to 5 Using a resin Varnish (Varnish) formulation composition having excellent heat resistance and low dielectric constant, prepared by adjusting the solid content of 65% using a solvent such as propylene glycol monomethyl ether (PM) or methyl ethyl ketone or acetone, glass fiber laminates were prepared by a known method, 7628 glass fiber cloths were impregnated with the above resin solution, dried at 170 ℃ (including the temperature of an impregnator) for several minutes, the minimum melt viscosity of the dried prepregs was adjusted to 4000 to 10000poise by adjusting and controlling the drying time, and 8 prepregs were laminated between two 35-um thick copper foils at 25kg/cm2Controlling a temperature rise program under pressure:
85℃→85℃→200℃→200℃→130℃
slowly cooling for 20min, 30min and 120min
The resulting film was hot-pressed to obtain a copper foil substrate having a thickness of 1.6 mm.
TABLE physical Properties of varnish composition and glass fiber laminate
Comparative examples 1 to 3
The formulation of the epoxy resin composition of the present invention is shown in Table II, wherein the epoxy resin copolymer of dicyclopentadiene-phenol and 2, 6-dimethylphenol is not used, and other low dielectric epoxy resins are used as comparative examples, wherein the composition of comparative example 1 is benzaldehyde-phenol epoxy resin (model NPPN-433 from south Asia plastics), the composition of comparative example 2 is 2, 6-dimethylphenol novolac epoxy resin (model NPPN-260 from south Asia plastics), and the composition of comparative example 3 is dicyclopentadiene-phenol epoxy resin (model NPPN-272H from south Asia plastics).
TABLE II physical Properties of comparative example varnish composition and glass fiber laminate
From the above test results, the dielectric constant Dk and the loss factor Df of the glass fiber laminate manufactured by substituting the copolymer epoxy resin of dicyclopentadiene-phenol of the invention and 2, 6-dimethylphenol into the formulation are lower than those of the benzaldehyde-phenol epoxy resin of comparative example 1 and 2, 6-dimethylphenol of comparative example 2, and the dicyclopentadiene-phenol epoxy resin of comparative example 3, and the Tg of the copolymer epoxy resin of dicyclopentadiene-phenol of the invention and 2, 6-dimethylphenol is higher than that of the formulations of comparative examples 1 to 3.
1. Water absorption test (PCT pressure cooker 2 hours)
The water absorption rate test method comprises cutting the etched substrate into 5cm2And (3) drying the square test piece in a 105 ℃ oven for 2hr, putting the test piece into a pressure cooker with the pressure cooker condition of 2atm × 120 ℃, and recording the weight difference of the test piece before and after the pressure cooker and the initial weight of the test piece as the water absorption rate after the pressure cooker is used for 120 min.
Solder-resistant and heat-resistant at 2.288 ℃ (2 hours in PCT pressure cooker)
The test method comprises immersing the above test piece in a solder furnace at 288 deg.C, and recording the time required for the test piece to explode and delaminate.
T-288 Heat resistance (copper-containing)
Using a thermal mechanical analyzer to analyze, wherein the testing method is that the copper-containing copper foil substrate is cut into 2 square test pieces with the size of 6.35mm, the square test pieces are baked in an oven at the temperature of 105 ℃ for 2 hours, the test pieces are placed in a test board of the thermal mechanical analyzer, after the test pieces are reset to zero, the thermal mechanical analyzer is heated to 288 ℃ at the speed of 10 ℃/min, and the time required by the delamination of the copper foil substrate of the test pieces is recorded.
4. Dielectric constant (Dielectric constant) test:
the test method comprises baking 5cm × 5cm square test piece of the glass fiber laminate with the ketone foil removed in a 105 deg.C oven for 2hr, measuring the thickness with a thickness meter, clamping the test piece in an impedance analyzer (Agilent E4991A), measuring the dielectric constant Dk data at 3 points, and averaging.
5. Consumption coefficient (dispensing factor) test:
the test method comprises baking 5cm × 5cm square test piece of the glass fiber laminate with the ketone foil removed in a 105 deg.C oven for 2hr, measuring the thickness with a thickness meter, clamping the test piece in an impedance analyzer (Agilent E4991A), measuring the consumption coefficient Df data at 3 points, and averaging.
6. Glass transition Temperature (Temperature of glass transition) test:
a Differential Scanning Calorimeter (DSC) was used, and the temperature increase rate was 20 ℃/min.
7. Molecular weight Mw:
GPC analysis was performed using a gel chromatograph, calibrated with a standard molecular weight polystyrene.
Claims (3)
1. A copolymer epoxy resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol, having the formula:
wherein 0< x ≦ 5, 0< y ≦ 5, and x, y are integers;
r represents: hydrogen, C1-C10 alkyl, phenyl or hydroxyphenyl.
2. The method for preparing the dicyclopentadiene-phenol-2, 6-dimethylphenol copolymer epoxy resin as claimed in claim 1, comprising the steps of;
step one, synthesizing dicyclopentadiene-phenol resin and 2, 6-dimethylphenol copolymer phenolic resin:
adding 1 mol of phenolic hydroxyl in (a1) dicyclopentadiene-phenol resin and 1-2.5 mol of (a2)2, 6-dimethylphenol into a medium-boiling-point low-volume water ratio solvent with a boiling point of more than 110 ℃, adding an acid catalyst, heating to 95-115 ℃, and adding 0.8 to 1.5 mol of 20 to 50% aqueous solution of an aldehyde compound dropwise to the reaction mixture, if the aldehyde compound is in a liquid state, the dropping reaction temperature is 95-115 ℃ without preparing an aqueous solution, the dropping reaction time of the aldehyde compound aqueous solution is 1-6 hours, using acid catalysts such as methanesulfonic acid, p-toluenesulfonic acid, oxalic acid and hydrochloric acid, wherein the dosage of the acid catalysts is 0.5-5% of that of dicyclopentadiene-phenol resin, aldehyde compounds such as formaldehyde, acetaldehyde, glyoxal and benzaldehyde are used, medium-boiling-point low-volume water ratio solvents selected from solvents such as methyl isobutyl ketone and toluene are used, and the dosage of the solvents is 5-20% of that of dicyclopentadiene-phenol resin; after the dropwise addition reaction is finished, performing ripening reaction for 30 minutes to 2 hours, and neutralizing the acid catalyst with alkali after the reaction is finished, wherein the alkali is sodium hydroxide, potassium hydroxide or amines; neutralizing until the pH value is 6-7, heating to remove the solvent and the 2, 6-dimethylphenol, keeping the temperature at 175-185 ℃, slowly reducing the vacuum degree until the temperature reaches 175-185 ℃ so as not to generate bumping, and finally keeping the vacuum degree at less than 5 torr; maintaining the temperature of 175-185 ℃ for 1 hour under the vacuum degree of <5 torr; continuously adding methyl isobutyl ketone or toluene as a solvent to dissolve the resin, adding water to carry out the steps of desalting, washing, filtering and desolventizing, and obtaining dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer phenolic resin after desolventizing;
step two, synthesizing copolymer epoxy resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol:
preparing copolymer epoxy resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol from copolymer phenolic resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol and excessive epichlorohydrin and sodium hydroxide under a common epoxidation condition, (1) pre-reacting, wherein the equivalent ratio of the copolymer phenolic resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol to the epichlorohydrin is 1: 1-8, adding a cosolvent which accounts for 10-40% of the amount of the copolymer of dicyclopentadiene-phenol resin and 2, 6-dimethylphenol, the cosolvent is selected from propylene glycol monomethyl ether or alcohol, adding 49.5% of sodium hydroxide, the equivalent ratio of the copolymer phenolic resin of dicyclopentadiene-phenol and 2, 6-dimethylphenol to the sodium hydroxide is 1: 0.05-0.2, and the pre-reaction temperature is 50-100 ℃, pre-reaction time is 2-4 hours; (2) in the main reaction, 49.5% of sodium hydroxide is added into the reactant in an equivalent ratio of 0.77-0.92, and the reaction temperature is 60-65 ℃, the vacuum degree is 160-190 torr, and the main reaction time is 2-5 hours, wherein 1 equivalent of dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer phenolic resin is dropwise added into the reactant; (3) removing excessive epichlorohydrin at the temperature of 160 ℃ and the vacuum degree of less than 5 torr; (4) adding a solvent to prepare a 30-50% solid resin solution, adding 20% sodium hydroxide to carry out a refining reaction at 70-90 ℃ for 1-3 hours, adding water to carry out desalting and separating, neutralizing, washing and separating, filtering the resin solution, and removing the solvent to obtain the dicyclopentadiene-phenol-2, 6-dimethylphenol copolymer epoxy resin as claimed in claim 1.
3. An epoxy resin varnish composition for glass fiber laminated plates comprises the following components:
(I) the dicyclopentadiene-phenol and 2, 6-dimethylphenol copolymer epoxy resin of claim 1, the amount of the epoxy resin is 30 to 80 percent of the total amount of the resin, and the total amount of the resin is equal to the sum of the component one to the component four;
(II) a polyfunctional or bifunctional or modified epoxy resin, which is used in an amount of 0to 25% based on the total amount of the resin, and is selected from the group consisting of an o-cresol novolac epoxy resin, a benzaldehyde-phenol polyfunctional epoxy resin, a dicyclopentadiene-phenol epoxy resin, a bisphenol A novolac epoxy resin, a tetraphenolethane novolac epoxy resin, a tris (hydroxyphenyl) methane novolac epoxy resin, a phosphorous epoxy resin, a2, 6-dimethylphenol novolac epoxy resin, a brominated epoxy resin, a bisphenol A epoxy resin, and a copolymer of an epoxy resin and an isocyanate;
(III) a hardening agent, the usage amount of which accounts for 15-60% of the total resin, is selected from bisphenol A type phenolic resin, dicyclopentadiene-phenol resin, benzaldehyde-phenol resin, melamine-phenol novolac resin, active ester hardening agent, styrene-maleic anhydride copolymer, bisphenol A type benzoxazine, bisphenol F type benzoxazine, dicyclopentadiene-phenol benzoxazine and polyphenyl ether; or any two or more of the aforementioned hardening agents;
(IV) a flame retardant, the usage amount of which accounts for 10-40% of the total resin, the flame retardant comprises a reaction type flame retardant and an additive type flame retardant, and the flame retardant is selected from a phosphorus-containing bisphenol A type phenolic hardener, wherein the phosphorus content is 5-10%, a phosphorus-containing bisphenol F type phenolic hardener, and hexaphenoxy cyclotriphosphazene, wherein the phosphorus content is 13.4%, the nitrogen content is 8%, and the bromine content is 58.5%;
(V) the filler accounts for 0-45% of the total formula varnish composition, and the formula varnish composition is equal to the sum of the first component and the fifth component in solid state calculation and is selected from silicon dioxide and aluminum hydroxide;
(VI) the hardening accelerator is used in an amount of 0.01 to 0.2 percent, and relative to the epoxy resin and the hardening agent, the sum of the component I and the component III is obtained; selected from dimethylimidazole, diphenylimidazole, diethyltetramethylimidazole, benzyldimethylamine;
and (VII) a solvent, the amount of which is 50-70% of the solid content of the varnish composition, and the solvent is selected from acetone, butanone, cyclohexanone, dimethoxyethanol, propylene glycol methyl ether, toluene and dimethylformamide.
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| CN103724596A (en) * | 2012-10-11 | 2014-04-16 | 新日铁住金化学株式会社 | Epoxy resin composition and condensate |
| US9512257B2 (en) * | 2013-03-28 | 2016-12-06 | Nan Ya Plastics Corporation | Halogen-free, nonflammable and high glass transition temperature phenolic resin-based curing agent and process for producing the same |
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| CN103724596A (en) * | 2012-10-11 | 2014-04-16 | 新日铁住金化学株式会社 | Epoxy resin composition and condensate |
| US9512257B2 (en) * | 2013-03-28 | 2016-12-06 | Nan Ya Plastics Corporation | Halogen-free, nonflammable and high glass transition temperature phenolic resin-based curing agent and process for producing the same |
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