Preparation method and application of end-capped modified polyphenyl phenolic resin

Abstract

The invention discloses a preparation method and application of end-capped modified polyphenyl phenolic resin, in the preparation method, polyphenyl phenolic resin is used as a main skeleton structure, and amine and halogenated olefin compound / anhydride compound react under the action of a catalyst to obtain the end-capped modified polyphenyl phenolic resin. According to the preparation method, the multi-branched terminated phenolic hydroxyl group of the multi-biphenyl phenolic resin is subjected to esterification and / or etherification reaction to be fully converted into the multifunctional unsaturated olefin-based resin taking unsaturated olefin as a terminated group, and the prepared multifunctional olefin-based terminated resin has the characteristics of good dielectric property, low thermal expansion, high heat resistance and the like; the method is suitable for electronic materials and composite materials, after resin reaction is finished, an anti-solvent method is adopted for precipitation and purification treatment, residual reactants and by-products influencing resin performance are removed, and excellent and stable product performance is kept. The phenolic resin can be widely applied to the electronic fields of high-frequency and high-speed electronic circuit copper-clad plates, electronic packaging materials, high-performance composite materials and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a preparation method and application of a capped modified polyphenyl phenol-formaldehyde resin. Background Art

[0002] With the development of the information industry and the electronics industry, digital circuits are gradually entering a stage of high speed and high frequency signal transmission. In order to process large-capacity information, the entire electronic system tends to develop in the direction of high frequency. In the use of electrical and electronic components, copper clad laminate technology is developing in the direction of thinness, high frequency and high speed, and the processing conditions are more stringent. In order to meet the performance requirements of high frequency and high speed, such as strong high-frequency signal penetration, lower attenuation speed and higher processing reliability, the industry has also placed higher requirements on the electrical insulation and heat resistance of copper clad laminate materials. Therefore, the circuit substrate resin insulation material is required to have excellent dielectric insulation, heat expansion resistance and high heat resistance to meet the reliability requirements and high-speed transmission requirements of circuit interconnection and electronic component installation.

[0003] Phenolic resins are mainly used to manufacture various plastics, coatings, adhesives and synthetic fibers. Phenolic resin-based materials can be applied to the production of copper-clad laminates to improve the high-temperature resistance of copper-clad laminates. Due to the strong resonance stability and aromaticity of the biphenyl structure, biphenyl phenolic resins exhibit good mechanical properties, electrical insulation and thermal stability in polymer materials, especially the non-polar olefin modification of its phenolic hydroxyl groups, which greatly improves the dielectric insulation, heat resistance and water absorption resistance of its cured products. In the existing disclosed biphenyl phenolic resin technology, patent CN 115362194 A performs allyl etherification modification on linear biphenyl phenolic resin to improve the dielectric properties and high thermal conductivity of the resin, and patent CN106795276A performs allyl ether modification on multifunctional vinyl resin biphenyl aralkyl phenolic varnish resin. However, in the above-mentioned technology, due to the insufficient etherification end-capping of the phenolic hydroxyl group, a large amount of phenolic hydroxyl group remains, and the hydroxyl equivalent is not more than 20000 g / mol, so the functionality of the olefin double bond is insufficient, which also increases the polarity of the product, and the biphenyl group accounts for a small proportion in the main chain structure of the molecule and the functionalized branching degree is low, which ultimately leads to the performance of the thermal expansion resistance, heat resistance and dielectric insulation of the polymer, which still has great deficiencies. Summary of the invention

[0004] In order to overcome the problems existing in the above-mentioned prior art, one of the purposes of the present invention is to provide a method for preparing a capped modified polyphenyl phenol-formaldehyde resin. A second purpose of the present invention is to provide a capped modified polyphenyl phenol-formaldehyde resin prepared by the above-mentioned preparation method. A third purpose of the present invention is to provide a metal-clad plate. A fourth purpose of the present invention is to provide the application of the above-mentioned capped modified polyphenyl phenol-formaldehyde resin and the metal-clad plate.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] The first aspect of the present invention provides a method for preparing a capped modified polyphenol-formaldehyde resin, comprising the following steps:

[0007] S1. Under the action of an alkali metal hydroxide catalyst, a polyphenyl phenol-formaldehyde resin and a halogenated olefin compound react in an organic solvent A to obtain a mixed solution containing a capped modified polyphenyl phenol-formaldehyde resin;

[0008] Alternatively, the polyphenyl phenol-formaldehyde resin and the acid anhydride compound are reacted in an organic solvent under the action of an amine catalyst to obtain a mixed solution containing the end-capped modified polyphenyl phenol-formaldehyde resin;

[0009] S2. Separating the end-capped modified polyphenyl phenol-formaldehyde resin in the mixed solution by an anti-solvent method.

[0010] Preferably, the preparation method of the polyphenyl phenol-formaldehyde resin comprises: reacting 4,4'-bis(chloromethyl)-1,1-biphenyl with a phenol compound to obtain the polyphenyl phenol-formaldehyde resin.

[0011] More preferably, the phenolic compound is selected from phenol, dimethylphenol, methylphenol, 2-methyl-6-phenylphenol, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl) ) octane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-n-butane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cycloheptane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclooctane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclononane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclodecane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclodecane, and 1,1-bis(4-hydroxy-3-methylphenyl)cycloundecane.

[0012] More preferably, the reaction can also use an acid catalyst, and the acid catalyst is selected from oxalic acid, formic acid, acetic acid, sulfuric acid, p-toluenesulfonic acid, and diethyl sulfate. The present invention uses a biphenyl type crosslinking agent with a halogenated methyl group, and can react appropriately even in the absence of an acid catalyst.

[0013] More preferably, the hydroxyl equivalent of the polyphenyl phenol-formaldehyde resin is 300-750 g / eq.

[0014] More preferably, the residual phenolic compound monomer of the polyphenyl phenol-formaldehyde resin is ≤2%.

[0015] More preferably, the weight average molecular weight of the polyphenyl phenol-formaldehyde resin is 3000-4000 g / mol.

[0016] Preferably, the alkali metal hydroxide catalyst is selected from at least one of potassium hydroxide and sodium hydroxide.

[0017] More preferably, the alkali metal hydroxide catalyst is added to the reaction system of reaction A in the form of an aqueous solution or a solid.

[0018] More preferably, the concentration of the alkali metal hydroxide aqueous solution is 5-55% (w / v).

[0019] Preferably, the halogenated olefin compound is selected from at least one of allyl chloride, allyl bromide, allyl iodide, p-chloromethylstyrene, p-bromomethylstyrene, p-iodomethylstyrene, o-chloromethylstyrene, o-bromomethylstyrene, o-iodomethylstyrene, m-chloromethylstyrene, m-bromomethylstyrene, m-iodomethylstyrene, methacryloyl chloride and acryloyl chloride.

[0020] Preferably, the temperature of reaction A is 25-100° C. and the time is 1-15 h.

[0021] More preferably, the temperature of reaction A is 50-90°C and the time is 3-13h.

[0022] Preferably, the molar ratio of the hydroxyl content of the polyphenyl phenol-formaldehyde resin to the halogenated olefin compound is 1:(1.2-3.6).

[0023] More preferably, the molar ratio of the hydroxyl content of the polyphenyl phenol-formaldehyde resin to the halogenated olefin compound is 1:(1.3-2.6).

[0024] Preferably, the molar ratio of the hydroxyl content of the polyphenyl phenol-formaldehyde resin to the alkali metal hydroxide catalyst is 1:(1.3-2.6).

[0025] Preferably, the hydroxyl equivalent of the end-capped modified polyphenyl phenol-formaldehyde resin obtained by reaction A is 80,000-200,000 g / eq.

[0026] Preferably, the amine catalyst is selected from at least one of 4-dimethylaminopyridine and 4-pyrrolidinopyridine.

[0027] Preferably, the acid anhydride compound is selected from at least one of acetic anhydride, succinic anhydride, allyl succinic anhydride, propionic anhydride, isobutyric anhydride, isobutenyl succinic anhydride, butenyl succinic anhydride, glutaric anhydride, adipic anhydride, acrylic anhydride, methacrylic anhydride and 4-vinylbenzoic anhydride.

[0028] Preferably, the temperature of reaction B is 80-120° C. and the time is 1-10 h.

[0029] More preferably, the temperature of reaction B is 90-110° C. and the time is 4-8 h.

[0030] Preferably, the molar ratio of the hydroxyl content of the polyphenyl phenol-formaldehyde resin to the acid anhydride compound is 1:(1.2-3).

[0031] More preferably, the molar ratio of the hydroxyl content of the polyphenyl phenol-formaldehyde resin to the acid anhydride compound is 1:(1.3-2.6).

[0032] Preferably, the mass ratio of the polyphenyl phenol-formaldehyde resin to the amine catalyst is 1:(0.01-0.1).

[0033] Preferably, the organic solvent is selected from at least one of methanol, n-propanol, n-butanol, acetone, methyl ethyl ketone, N,N-dimethylformamide, dimethyl sulfoxide, toluene, xylene, and cyclohexane.

[0034] Preferably, the anti-solvent used in the anti-solvent method is at least one selected from acetone, hexane and methanol.

[0035] More preferably, the anti-solvent is methanol, and the mass ratio of methanol to the organic solvent is 50:(1-10).

[0036] Preferably, step S2 further comprises: drying the separated end-capped modified polyphenyl phenol-formaldehyde resin at 50-70°C.

[0037] The second aspect of the present invention provides a capped modified polyphenyl phenol-formaldehyde resin prepared by the preparation method described in the first aspect.

[0038] The third aspect of the present invention provides a metal-clad plate, characterized in that it includes a semi-cured plate and a metal plate, and the metal plates are arranged on both sides of the semi-cured plate; the raw materials for preparing the semi-cured plate include reinforcing fibers and a resin composition; the raw materials for preparing the resin composition include the end-capped modified polyphenol-formaldehyde resin described in the first aspect.

[0039] Preferably, the raw materials for preparing the resin composition further include a cross-linking curing agent and an inorganic filler.

[0040] More preferably, the cross-linking curing agent is selected from at least one of dibenzoyl peroxide, methyl ethyl ketone peroxide, dicyandiamide, 2-methyl-4-ethylimidazole, dicumyl peroxide, and triallyl isocyanurate.

[0041] More preferably, the inorganic filler is at least one selected from talc, aluminum hydroxide, aluminum oxide, silicon powder, and silicon dioxide.

[0042] More preferably, the resin composition is composed of the following components in parts by mass: 70-90 parts of end-capped modified polyphenyl phenolic resin, 15-30 parts of cross-linking curing agent and 25-35 parts of inorganic filler.

[0043] Preferably, the metal-clad plate is prepared by a preparation method comprising the following steps:

[0044] The resin composition is mixed with an organic solvent to obtain a resin composition solution, the resin composition solution is coated on the reinforcing fiber, and solidified to obtain a semi-cured sheet; the semi-cured sheet is pressed together with a metal plate to obtain a metal-clad plate.

[0045] The fourth aspect of the present invention provides the use of the end-capped modified polyphenol-formaldehyde resin of the second aspect or the metal-clad laminate of the third aspect in the preparation of electronic products.

[0046] The beneficial effects of the present invention are:

[0047] (1) The present invention provides a method for preparing a capped modified polyphenolic resin, wherein the polyphenolic resin is used as the main skeleton structure, and is reacted with a halogenated olefin compound / anhydride compound, so that the multi-branched capped phenolic hydroxyl groups of the polyphenolic resin are fully converted into a multifunctional unsaturated olefin-based resin with unsaturated olefins as the capping groups after esterification and / or etherification reaction. Through the formula and process design of the modification reaction, the phenolic hydroxyl groups are more fully converted into olefin groups, and the residual phenolic hydroxyl groups are less than 5%, wherein the full conversion of the polar groups to non-polar groups greatly improves the dielectric insulation and water absorption resistance of the product, and also means that the increase in the functionality of the olefin groups makes the mechanical properties and heat resistance more excellent. After the resin reaction is completed, the preparation method of the present invention adopts an anti-solvent method for precipitation and purification treatment to remove residual reactants and by-products that affect the resin performance, thereby maintaining excellent and stable product performance.

[0048] (2) The present invention provides a multifunctional olefin-terminated resin prepared by the above-mentioned preparation method, which has good dielectric properties, low thermal expansion and high heat resistance, and is suitable for use in electronic materials and composite materials. The multi-branched skeleton structure formed by self-bridging of polyphenyls has excellent mechanical properties, low thermal expansion and high heat resistance, and the molecular design of the multifunctional olefin-based branched end-capping further optimizes and improves its various properties after curing.

[0049] (3) The olefin-modified polyphenyl phenolic resin cured product of the present invention has excellent comprehensive characteristics such as lower dielectric constant, higher Tg, lower CTE, lower water absorption and better heat resistance, and thus better meets the performance requirements of high frequency and high speed, such as strong high-frequency signal penetration, lower attenuation rate and higher multilayer board processing reliability. At the same time, it can also meet the performance requirements of other fields such as low thermal expansion coefficient, high thermal stability and excellent mechanical properties, and can be widely used in high-frequency and high-speed electronic circuit copper-clad laminates, electronic packaging materials, high-performance composite materials, and aerospace special materials. DETAILED DESCRIPTION

[0050] The present invention is further described in detail below through specific examples. The raw materials used in the following examples, unless otherwise specified, can be obtained from conventional commercial sources or prepared and separated by simple synthesis; the processes used, unless otherwise specified, are conventional processes in the art.

[0051] Example 1

[0052] This embodiment provides a capped modified polyphenyl phenol-formaldehyde resin, and the synthesis steps are as follows:

[0053] 1. Preparation of polyphenolic resin: Toluene is used as the reaction solvent. 1 mol (251 g) of 4,4'-bis (chloromethyl) -1,1-biphenyl, 1 mol (251 g) of 2,6-dimethylphenol and 250 g of toluene are added to the reactor. The reaction temperature is set to 95°C and the reaction time is 5 h. After the reaction is completed, the reaction is distilled at 130°C for 1 h to remove the reaction solvent toluene and the by-product hydrochloric acid. The reaction is cooled to obtain polyphenolic resin. The technical indicators are: hydroxyl equivalent is 368 g / eq, the reactant 2,6-dimethylphenol remains 0.8% (GPC), and the weight average molecular weight is 3528 g / mol (GPC).

[0054] 2. Preparation of end-capped modified polyphenyl phenolic resin: 184g (equivalent to 0.5mol of hydroxyl content), 250g of toluene, and 0.7mol (107g) of chloromethylstyrene are added into a reactor, and the temperature is raised to 65°C to dissolve. Based on the molar content of hydroxyl groups in the polyphenyl phenolic resin, 0.7mol (58.3g) of 48% sodium hydroxide aqueous solution is added dropwise, and the mixture is kept at 70°C for reaction for 8 hours; phosphoric acid is added to the obtained resin mixture to adjust the pH to 6 for neutralization, and the aqueous phase is separated and removed to obtain a styrene-terminated copolymer mixed solution; 2500g of methanol is added to the continuously stirred mixed solution, and the end-capped copolymer is precipitated from the solution, separated, and then dried at 60°C under vacuum for 12 hours. The hydroxyl equivalent of the obtained vinyl resin is 161260.2g / eq, and the total chlorine is 530ppm.

[0055] Example 2

[0056] This embodiment provides a capped modified polyphenyl phenol-formaldehyde resin, and the synthesis steps are as follows:

[0057] 184 g of the polyphenyl phenol-formaldehyde resin obtained in Example 1 (equivalent to a hydroxyl content of 0.5 mol), 250 g of toluene, 11 g of 4-dimethylaminopyridine and 1 mol (154 g) of methacrylic anhydride were added to a reactor and reacted at 95° C. for 6 hours to obtain an allyl-terminated copolymer mixed solution; 2500 g of methanol was added to the continuously stirred mixed solution, and the blocked copolymer was precipitated from the solution, separated, and then dried at 60° C. under vacuum for 12 hours; the hydroxyl equivalent of the obtained methacrylic resin was 121233.5 g / eq, and the methacrylic acid content of the reaction product was 0.16% (GPC).

[0058] Example 3

[0059] This embodiment provides a capped modified polyphenyl phenol-formaldehyde resin, and the synthesis steps are as follows:

[0060] 184g of the polyphenyl phenolic resin obtained in Example 1 (equivalent to 0.5mol of hydroxyl content), 250g of toluene and 1.25mol (95g) of chloropropylene were placed in a reactor, and the temperature was raised to 65°C to dissolve it; 1.25mol (104g) of 48% sodium hydroxide aqueous solution was added dropwise, and the mixture was reacted at 65°C for 13 hours; phosphoric acid was added to the obtained resin mixture to adjust the pH to 6 for neutralization, and the aqueous phase was separated and removed to obtain an allyl-terminated copolymer mixed solution; 2500g of methanol was added to the continuously stirred mixed solution, and the blocked copolymer was precipitated from the solution, separated, and then dried at 60°C under vacuum for 12 hours. The hydroxyl equivalent of the obtained allyl resin was 13573.1g / eq, and the total chlorine was 631ppm.

[0061] Example 4

[0062] This embodiment provides a capped modified polyphenyl phenol-formaldehyde resin, and the synthesis steps are as follows:

[0063] 184g of the polyphenyl phenolic resin (equivalent to 0.5mol of hydroxyl content), 250g of n-butanol and 0.7mol (107g) of chloromethylstyrene prepared in Example 1 were placed in a reactor, and the temperature was raised to 80°C to dissolve it; 0.7mol (58.3g) of 48% sodium hydroxide aqueous solution was added dropwise, and the reaction was carried out at 70°C for 3 hours; phosphoric acid was added to the obtained resin mixture to adjust the pH to 6 for neutralization, and the water phase was separated and removed to obtain a styrene-terminated copolymer mixed solution; 2500g of methanol was added to the continuously stirred mixed solution, and the blocked copolymer was precipitated from the solution, separated, and then dried at 60°C under vacuum for 12 hours. The hydroxyl equivalent of the obtained vinyl resin A was 15368.0g / eq, and the total chlorine was 573ppm.

[0064] Comparative Example 1

[0065] This comparative example provides a modified polyphenyl phenol-formaldehyde resin, and the synthesis steps thereof are as follows:

[0066] 1. Toluene is used as the reaction solvent. 1 mol (251 g) of 4,4'-bis (chloromethyl) -1,1-biphenyl, 2.5 mol (275 g) of hydroquinone and 250 g of toluene are added to the reactor. The reaction temperature is set to 95°C and the reaction time is 5 h. After the reaction is completed, the reaction is distilled at 130°C for 1 h to remove the reaction solvent toluene and the by-product hydrochloric acid, and cooled to obtain a biphenyl phenolic resin composition. The technical indicators are: hydroxyl equivalent is 110.9 g / eq, the reactant hydroquinone residue is 11.3% (GPC), and the weight average molecular weight is 836 g / mol (GPC).

[0067] 2. Add 56g of biphenyl phenolic resin (equivalent to 0.5mol of hydroxyl content), 150g of toluene, and 0.7mol (107g) of chloromethylstyrene obtained in Synthesis Example 2 into a reactor, heat to 65°C to dissolve it; add 0.7mol (58.3g) of 48% sodium hydroxide aqueous solution dropwise, and react at 70°C for 8 hours. Add phosphoric acid to the obtained resin mixture to adjust the pH to 6 for neutralization, separate and remove the water phase to obtain a styrene-terminated copolymer mixed solution; add 2000g of methanol to the continuously stirred mixed solution, and precipitate the blocked copolymer from the solution, separate, and then dry at 60°C under vacuum for 12 hours. The hydroxyl equivalent of the obtained vinyl resin is 135406.0g / eq, and the total chlorine is 673ppm.

[0068] Comparative Example 2

[0069] This comparative example provides a modified polyphenyl phenol-formaldehyde resin, and its synthesis steps are similar to those of Example 1, except for the amount of alkali metal hydroxide catalyst used. The specific steps are as follows:

[0070] 184g of the polyphenyl phenolic resin obtained in Example 1 above (equivalent to 0.5mol of hydroxyl content), 250g of toluene and 0.7mol (107g) of chloromethylstyrene were placed in a reactor, and the temperature was raised to 65°C to dissolve it; 0.6mol (50g) of 48% sodium hydroxide aqueous solution was added dropwise, and the reaction was carried out at 70°C for 8 hours. Phosphoric acid was added to the obtained resin mixture to adjust the pH to 6 for neutralization, and the aqueous phase was separated and removed to obtain a styrene-terminated copolymer mixed solution; 2500g of methanol was added to the continuously stirred mixed solution, and the blocked copolymer was precipitated from the solution, separated, and then dried at 60°C under vacuum conditions for 12 hours. The hydroxyl equivalent of the obtained vinyl resin was 11363.1g / eq, and the total chlorine was 586ppm.

[0071] Comparative Example 3

[0072] This comparative example provides a modified polyphenyl phenol-formaldehyde resin, and its synthesis steps are similar to those of Example 1, except that the amount of the halogenated olefin compound is changed. The specific steps are as follows:

[0073] 184g of the polyphenyl phenol-formaldehyde resin obtained in Example 1 above (equivalent to 0.5mol of hydroxyl content), 250g of toluene and 0.6mol (91.7g) of chloromethylstyrene were placed in a reactor, and the temperature was raised to 65°C to dissolve it; 0.7mol (58.3g) of 48% sodium hydroxide aqueous solution was added dropwise, and the reaction was carried out at 70°C for 8 hours. Phosphoric acid was added to the obtained resin mixture to adjust the pH to 6 for neutralization, and the aqueous phase was separated and removed to obtain a styrene-terminated copolymer mixed solution; 2500g of methanol was added to the continuously stirred mixed solution, and the blocked copolymer was precipitated from the solution, separated, and then dried at 60°C under vacuum conditions for 12 hours. The hydroxyl equivalent of the obtained vinyl resin was 15561.3g / eq, and the total chlorine was 735ppm.

[0074] Comparative Example 4

[0075] This comparative example provides a modified polyphenyl phenolic resin, and the specific steps are as follows:

[0076] 184g of the polyphenyl phenol-formaldehyde resin obtained in Example 1 above (equivalent to 0.5mol of hydroxyl content), 250g of toluene and 0.7mol (107g) of chloromethylstyrene were placed in a reactor, and the temperature was raised to 65°C to dissolve it; 0.7mol (58.3g) of 48% sodium hydroxide aqueous solution was added dropwise, and the reaction was carried out for 8 hours. Phosphoric acid was added to the obtained resin mixed solution to adjust the pH to 5-7 for neutralization, and the aqueous phase was separated and removed to obtain a styrene-terminated copolymer mixed solution with a hydroxyl equivalent of 161260.2g / eq and a total chlorine content of 3573ppm.

[0077] Comparative Example 5

[0078] This comparative example provides a modified polyphenyl phenolic resin, and the specific steps are as follows:

[0079] 0.5 mol (184 g) of the polyphenyl phenol-formaldehyde resin obtained in Example 1, 250 g of toluene, 11 g of 4-dimethylaminopyridine, and 1 mol (154 g) of methacrylic anhydride were added into a reactor and reacted at 95° C. for 6 hours to obtain a methacrylic-terminated copolymer mixed solution. Sodium bicarbonate was added to the obtained resin mixed solution to adjust the pH to 8 for neutralization, and the aqueous phase was separated and removed to obtain a methallyl resin solution having a hydroxyl equivalent of 81336.7 g / eq and a methacrylic acid content of 3.6% (GPC).

[0080] The measurement methods of hydroxyl equivalent, GPC and total chlorine of the above resin are as follows:

[0081] GPC determination method: Weigh 0.01g of the sample to be tested and dissolve it in 10mL of tetrahydrofuran, and use Waters gel chromatography (GPC) for testing. The chromatographic columns are Agilent MIXED-D chromatographic column and Shodex KF802 chromatographic column used in series, the mobile phase is tetrahydrofuran, and the flow rate is 1mL / min.

[0082] Hydroxyl equivalent measurement method: 7.8 mL of acetic anhydride and 35 mL of pyridine are used to prepare a mixed solution, 5 mL of the mixed solution is mixed with 1 g of the sample to be tested and reacted at 160°C for 1 hour, 1-1.5 mL of distilled water is added, the reaction is carried out for 15 minutes, and the sample solution and the blank control group are diluted with 0.5 M KOH solution respectively for potentiometric titration, wherein the potentiometric measuring instrument is the 888titrando equipment of Wantong Company, the electrode is the 6.0229.100Solvotrode equipment of Wantong Company, and the blank control group is not added with the sample to be tested.

[0083] Substitute the measured values ​​of the test solution and the blank control group into the following formula to calculate the hydroxyl equivalent:

[0084] OH value (KOH mg / g) = 28.05 × (BV) × F / mass of sample to be tested

[0085] Hydroxyl equivalent (g / eq) = 26110 / OH value

[0086] Wherein, B is the measured value of the blank control solution, V is the measured value of the sample solution, and F is the concentration of the titrated KOH (EtOH) solution (mol / L).

[0087] Total chlorine: 1.0 g of the sample is dissolved in 25 ml of butyl carbitol, 25 ml of 1N-KOH propylene glycol solution is added, the mixture is heated under reflux for 10 minutes, the mixture is cooled to room temperature, 100 ml of 80% acetone water is further added, and the total chlorine is measured by potentiometric titration with 0.002N-AgNO3 aqueous solution.

[0088] Comparing the polyphenyl phenol-formaldehyde resins of Example 1 and Comparative Example 1, the reactant phenolic compounds are excessive in the synthesis formula, resulting in a small molecular weight of the product, a high content of phenolic reactant monomers, and a low degree of branching.

[0089] Comparison of the hydroxyl equivalents of Example 1 and Comparative Examples 2-3 indicates that insufficient addition of olefin halide or alkaline catalyst will result in significantly low hydroxyl equivalent and insufficient conversion of hydroxyl groups.

[0090] Comparison of Examples 1-5 and Comparative Examples 4-5 shows that the anti-solvent precipitation cleaning process can effectively separate excess reactants and low-molecular reaction by-products, ensuring stable product quality and excellent performance.

[0091] Experimental testing

[0092] The modified polyphenyl phenolic resins of Examples 1-2 and Comparative Examples 1-5 were pressed into glass fiber copper clad laminates for performance testing:

[0093] 1. Preparation method of glass fiber copper clad laminate

[0094] Preparation of resin glue: Calculated by solid weight, take 80 parts of the olefin-based resin of the embodiment or comparative example, 20 parts of triallyl isocyanurate (Hubei Jusheng), 0.5 parts of diisopropylbenzene peroxide, and 30 parts of spherical silica, dissolve them in toluene solvent, and prepare a resin solution with a solid content of 50% under sufficient stirring.

[0095] The resin solution was impregnated with a 2116 fiberglass cloth and baked at 130°C for 3 minutes to form a prepreg. The prepreg had a glue content of 55±5%.

[0096] Take 6 prepregs, stack them neatly, cover both sides with copper foil, place them between stainless steel plates, and then put them in a vacuum press at 210±3℃ and 35kgf / cm 2The glass fiber copper clad laminate was produced by hot pressing for 180 minutes under the conditions.

[0097] 2. Test methods

[0098] The test items include glass transition temperature (Tg), coefficient of thermal expansion (CTE), water absorption, dielectric loss factor (Df) and thermal decomposition degree (Td). The test methods for each test item are as follows:

[0099] Glass transition temperature (Tg): measured using DMA test method specified in IPC-TM-650 2.4.24.4.

[0100] Coefficient of Thermal Expansion (CTE): Tested in accordance with IPC-TM-650 2.4.41 standard.

[0101] Water absorption: Tested in accordance with IPC-TM-650 2.6.2.1 standard.

[0102] Dielectric loss factor (Df): Tested in accordance with IPC-TM-650 2.5.5.9, with a test frequency of 1MHz.

[0103] Thermal decomposition degree (Td): Tested using TGA in accordance with IEC61189-2-807:2021 standard.

[0104] 3. The performance test results are shown in Table 1:

[0105] Table 1 Performance test summary

[0106]

[0107] As can be seen from Table 1, the composite resin pressed glass fiber copper clad laminate (i.e., Application Examples 1-2) prepared from the olefin-based polyphenyl resin synthesized in Examples 1 and 2 of the present invention has higher heat resistance, better water absorption resistance and dielectric properties than the olefin-based resin synthesized in Comparative Examples 1-5 (i.e., Application Examples 3-7). Among them, Application Examples 1, Application Examples 2 and Application Examples 3 are compared, and Application Examples 1 and 2 show that the skeleton structure obtained in Example 1 has better heat resistance and dielectric insulation than the skeleton structure obtained in Example 2. Application Example 3 has obviously insufficient application properties such as heat resistance and dielectric insulation due to the small molecular weight of the product, high content of phenolic reactant monomers and low degree of branching; Application Examples 4 and Application Examples 5 show that the conversion of phenolic hydroxyl groups to olefin groups is insufficient, which will make the application properties such as heat resistance and dielectric insulation of the cured product obviously insufficient; Application Examples 6 and Application Examples 7 show that the residues of reactants and low molecular weight reaction byproducts will affect the heat resistance and dielectric insulation of the product.

[0108] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a capped modified polyphenyl phenol-formaldehyde resin, characterized in that: The steps include: S1. Under the action of an alkali metal hydroxide catalyst, a polyphenyl phenol-formaldehyde resin and a halogenated olefin compound react in an organic solvent A to obtain a mixed solution containing a capped modified polyphenyl phenol-formaldehyde resin; Alternatively, the polyphenyl phenol-formaldehyde resin and the acid anhydride compound are reacted in an organic solvent under the action of an amine catalyst to obtain a mixed solution containing the end-capped modified polyphenyl phenol-formaldehyde resin; S2. Separating the end-capped modified polyphenyl phenol-formaldehyde resin in the mixed solution by an anti-solvent method.

2. The method for preparing the end-capped modified polyphenol-formaldehyde resin according to claim 1, wherein: The preparation method of the polyphenyl phenol-formaldehyde resin comprises: 4,4'-bis(chloromethyl)-1,1-biphenyl reacts with a phenol compound to prepare the polyphenyl phenol-formaldehyde resin.

3. The method for preparing the end-capped modified polyphenol-formaldehyde resin according to claim 1, characterized in that: The alkali metal hydroxide catalyst is selected from at least one of potassium hydroxide and sodium hydroxide; And / or, the halogenated olefin compound is selected from at least one of allyl chloride, allyl bromide, allyl iodide, p-chloromethylstyrene, p-bromomethylstyrene, p-iodomethylstyrene, o-chloromethylstyrene, o-bromomethylstyrene, o-iodomethylstyrene, m-chloromethylstyrene, m-bromomethylstyrene, m-iodomethylstyrene, methacryloyl chloride and acryloyl chloride.

4. The method for preparing the end-capped modified polyphenol-formaldehyde resin according to claim 1, wherein: The temperature of the reaction A is 25-100°C; and / or the time is 1-15h; And / or, the molar ratio of the hydroxyl content of the polyphenyl phenol-formaldehyde resin to the halogenated olefin compound is 1:(1.2-3.6).

5. The method for preparing the end-capped modified polyphenol-formaldehyde resin according to claim 1, characterized in that: The amine catalyst is selected from at least one of 4-dimethylaminopyridine and 4-pyrrolidinopyridine; And / or, the acid anhydride compound is selected from at least one of acetic anhydride, succinic anhydride, allyl succinic anhydride, propionic anhydride, isobutyric anhydride, isobutenyl succinic anhydride, butenyl succinic anhydride, glutaric anhydride, adipic anhydride, acrylic anhydride, methacrylic anhydride and 4-vinylbenzoic anhydride.

6. The method for preparing the end-capped modified polyphenol-formaldehyde resin according to claim 1, characterized in that: The temperature of the reaction B is 50-100°C; and / or the time is 1-10h; And / or, the molar ratio of the hydroxyl content of the polyphenyl phenol-formaldehyde resin to the acid anhydride compound is 1:(1.2-3).

7. The end-capped modified polyphenyl phenol-formaldehyde resin obtained by the preparation method according to any one of claims 1 to 6.

8. A metal clad plate, characterized in that: It comprises a semi-cured plate and a metal plate, wherein the metal plates are arranged on both sides of the semi-cured plate; the raw materials for preparing the semi-cured plate comprise reinforcing fibers and a resin composition; the raw materials for preparing the resin composition comprise the end-capped modified polyphenol-formaldehyde resin described in claim 7.

9. The metal-clad plate according to claim 8, characterized in that: The raw materials for preparing the resin composition also include a cross-linking curing agent and an inorganic filler.

10. Use of the end-capped modified polyphenyl phenol-formaldehyde resin according to claim 7 or the metal-clad plate according to any one of claims 8 to 9 in the preparation of electronic products.

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