CN117510770A - Modified phenolic resin and preparation method and application thereof - Google Patents
Modified phenolic resin and preparation method and application thereof Download PDFInfo
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- CN117510770A CN117510770A CN202311364579.5A CN202311364579A CN117510770A CN 117510770 A CN117510770 A CN 117510770A CN 202311364579 A CN202311364579 A CN 202311364579A CN 117510770 A CN117510770 A CN 117510770A
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 23
- 239000005011 phenolic resin Substances 0.000 claims abstract description 23
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920003986 novolac Polymers 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
- 150000001299 aldehydes Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000005022 packaging material Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- -1 bisphenol a Chemical compound 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 125000005375 organosiloxane group Chemical group 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- 229940100630 metacresol Drugs 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000000463 material Substances 0.000 abstract description 12
- 239000003822 epoxy resin Substances 0.000 abstract description 9
- 229920000647 polyepoxide Polymers 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 230000009477 glass transition Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010292 electrical insulation Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- 229920006336 epoxy molding compound Polymers 0.000 description 12
- 238000004806 packaging method and process Methods 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- QNHCWLYFWBZVOM-UHFFFAOYSA-N benzoic acid;hydrate Chemical compound O.OC(=O)C1=CC=CC=C1 QNHCWLYFWBZVOM-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified phenolic resin and a preparation method and application thereof. The preparation method of the modified phenolic resin comprises the following steps: (1) preparing a novolac resin; (2) preparing a nitrogen-containing phenolic resin; (3) Mixing the linear phenolic resin prepared in the step (1), the nitrogenous phenolic resin prepared in the step (2) and the organic siloxane, adding a weak acid aqueous solution, adjusting the pH value to be 5-7, heating the reaction system to 95-100 ℃ for stirring, and adding a solvent for dissolving after the stirring is completed, thus obtaining the modified phenolic resin. When the modified phenolic resin prepared by the invention is used for curing epoxy resin, the cured product has excellent performance, the glass transition temperature is obviously improved, the polarity of the resin is reduced, the heat resistance, corrosion resistance, electrical insulation and mechanical properties are improved, and the electromagnetic shielding effect and stability of the EMC material are improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified phenolic resin and a preparation method and application thereof.
Background
The semiconductor chip is the core of the semiconductor microelectronic technology, the integration level is rapidly increased due to the development of the modern electronic technology, the heat generated per second on each chip is up to more than 10J, and meanwhile, the chips work under severe environments (water vapor, chemical medium, radiation and vibration), so that the chips are required to be protected more specifically, and the selection of excellent packaging materials is particularly critical. According to the difference of packaging materials, the packaging materials can be divided into three categories of plastic packaging, ceramic packaging and metal packaging, at present, the plastic packaging occupies more than 90 percent of the semiconductor packaging, and more than 90 percent of the plastic packaging materials are all from Epoxy Molding Compounds (EMC), epoxy resin is taken as matrix resin, high-performance phenolic resin is taken as curing agent, filler such as silica powder and the like is added, and molding compounds formed by mixing various additives are added. The plastic packaging process is to squeeze EMC into a die cavity by a transfer molding method and embed a semiconductor chip therein, and simultaneously, the semiconductor chip is crosslinked, solidified and molded to form a semiconductor device with a certain structural shape.
At present, most of plastic packaging materials are prepared by curing phosphorus-containing epoxy resin by taking phosphorus-containing phenolic resin as a curing agent to achieve FV-0 level, and the method has high cost, glass transition temperature of about 150 ℃ and heat resistance of 5min. A small amount of dicyandiamide is used as a curing agent to cure the phosphorus-containing epoxy resin, and part of phosphate and phosphorus-containing organic filler are added to achieve FV-0 level, so that the method has the lowest performance, the glass transition temperature is less than 130 ℃, the heat resistance is 2min, and the technical requirements of lead-free semiconductors are not met. Therefore, how to increase the glass transition temperature and heat resistance of plastic packaging materials is a problem to be solved in the plastic packaging field.
Disclosure of Invention
In order to overcome the problems, the invention provides a modified phenolic resin and a preparation method and application thereof. When the modified phenolic resin prepared by the invention is used for curing epoxy resin, the cured product has excellent performance, the glass transition temperature is obviously improved, the polarity of the resin is reduced, the heat resistance, corrosion resistance, electrical insulation and mechanical properties are improved, and the electromagnetic shielding effect and stability of the EMC material are improved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a process for the preparation of a modified phenolic resin, the process comprising the steps of:
(1) Adding an acidic aqueous solution into phenolic substances and aldehyde substances, heating a reaction system to 700100 ℃ for reaction for 506 hours, adding deionized water when detecting that free aldehyde in an upper aqueous solution meets a set standard, stirring, standing after stirring is completed, and removing solvent water to obtain the novolac resin;
(2) Adding alkaline aqueous solution into phenolic substances, aldehyde substances and nitrogen-containing compounds to adjust the pH value of the solution to 507, heating the reaction system to 65065 ℃ for reaction for 102h, cooling to 45060 ℃ when the detected central control viscosity meets the set standard, and dehydrating to obtain the nitrogen-containing phenolic resin;
(3) Mixing the linear phenolic resin prepared in the step (1), the nitrogenous phenolic resin prepared in the step (2) and the organic siloxane, adding a weak acid aqueous solution, adjusting the pH value to 507, heating the reaction system to 950100 ℃, stirring, adding a solvent after stirring is completed, and dissolving to obtain the modified phenolic resin.
In a second aspect of the present invention, there is provided a modified phenolic resin prepared by the above-described preparation method.
In a third aspect of the invention there is provided the use of the modified phenolic resin described above as a curing agent in an electrical packaging material.
The invention has the beneficial effects that:
according to the invention, the linear phenolic resin and the nitrogenous phenolic resin are synthesized in sections, the formed nitrogenous resin contains a high-rigidity long-chain block structure, then organic silicon is introduced into the phenolic resin through a grafting reaction, active groups are introduced, the modified product of the nitrogenous phenolic resin realizes effective dispersion of the organic siloxane in the phenolic resin, the steric hindrance is reduced, the nucleophilic addition of phenolic hydroxyl groups and epoxy groups is promoted due to high bond energy in a crosslinking system, when the nitrogenous phenolic resin is used for curing the epoxy resin, the performance of the cured product is excellent, the glass transition temperature is obviously improved, the polarity of the resin is reduced, the heat resistance, the corrosion resistance, the electrical insulation property and the mechanical property are improved, and the electromagnetic shielding effect and the stability of the EMC material are improved.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In a first exemplary embodiment of the present invention, there is provided a method for preparing a modified phenolic resin, the method comprising the steps of:
(1) Adding an acidic aqueous solution into phenolic substances and aldehyde substances, heating a reaction system to 700100 ℃ for reaction for 506 hours, adding deionized water when detecting that free aldehyde in an upper aqueous solution meets a set standard, stirring, standing after stirring is completed, and removing solvent water to obtain the novolac resin;
(2) Adding alkaline aqueous solution into phenolic substances, aldehyde substances and nitrogen-containing compounds to adjust the pH value of the solution to 507, heating the reaction system to 65065 ℃ for reaction for 102h, cooling to 45060 ℃ when the detected central control viscosity meets the set standard, and dehydrating to obtain the nitrogen-containing phenolic resin;
(3) Mixing the linear phenolic resin prepared in the step (1), the nitrogenous phenolic resin prepared in the step (2) and the organic siloxane, adding a weak acid aqueous solution, adjusting the pH value to 507, heating the reaction system to 950100 ℃, stirring, adding a solvent after stirring is completed, and dissolving to obtain the modified phenolic resin.
In one or more embodiments, in the step (1) and the step (2), the phenolic substance includes one or more of phenol, bisphenol a, bisphenol F, ortho-phenol, meta-cresol, para-cresol, or para-diphenol.
In one or more embodiments, in the step (1) and the step (2), the aldehyde substance includes one or more of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde.
In one or more embodiments, in the step (1), the solute in the acidic aqueous solution includes one or more of oxalic acid, citric acid, acetic acid, benzoic acid, benzenesulfonic acid, or salicylic acid.
In one or more embodiments, in the step (1), the mass ratio of the phenolic substance to the aldehyde substance is 1.5: (0.601).
In one or more embodiments, in step (1), the acidic aqueous solution has a mass of 204%, preferably 3%, of the total mass of phenolic material.
In one or more embodiments, in step (1), the mass fraction of solute in the acidic aqueous solution is 50%060%.
In one or more embodiments, in step (1), the reaction process comprises: firstly, 10% of the total mass of the acidic aqueous solution is added, the reaction system is heated to 60 ℃, then the temperature is kept for 2 hours, the rest acidic aqueous solution is added, the reaction system is controlled to be slowly heated to 90 ℃ within 30040 minutes, and the temperature is kept for 2.5 hours.
In one or more embodiments, in step (1), the set criterion is less than 10000ppm free aldehyde in the aqueous upper layer solution.
In one or more embodiments, in step (1), the deionized water is present in an amount of 20040%, preferably 30% of the total mass of phenolic material.
In one or more embodiments, in step (1), the time of stirring after adding deionized water is 25040min, preferably 30min.
In one or more embodiments, in the step (1), the time for standing after the completion of the stirring is 30050min, preferably 40min.
In one or more embodiments, in the step (2), the solute in the alkaline aqueous solution is ammonia or triethylamine.
In one or more embodiments, in step (2), the nitrogen-containing compound is one of urea or melamine.
In one or more embodiments, in the step (2), the mass ratio of the phenolic substance, the aldehyde substance, and the nitrogen-containing compound is (0.700.9): 5: (0.601.4).
In one or more embodiments, in step (2), the reaction process comprises: heating the reaction system to 66072 ℃, stopping heating, naturally heating to 60 ℃ and preserving heat for reaction for 1 hour.
In one or more embodiments, in the step (2), the setting criteria are: the viscosity was controlled at 30035mPa.s/25 ℃.
In one or more embodiments, in the step (2), when the temperature is reduced to 50 ℃, dehydration is performed, the medium-control viscosity is 60070mPa.s/25 ℃, and the dehydration is finished.
In one or more embodiments, in step (3), the mass ratio of the novolac resin prepared in step (1) to the nitrogen-containing novolac resin and organosiloxane prepared in step (2) is 50060:40050:10015.
In one or more embodiments, in step (3), the solvent is one or two of methanol, acetone, or butanone.
In a second exemplary embodiment of the present invention, a modified phenolic resin prepared by the above-described preparation method is provided.
In a third exemplary embodiment of the present invention, there is provided the use of the modified phenolic resin described above as a curing agent in an electrical packaging material.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1: preparation of modified phenolic resin
(1) Adding 1500g of phenol and 1000g of formaldehyde solution (the mass fraction of solute is 37%) into a reaction kettle, adding 45g of oxalic acid aqueous solution (the mass fraction of solute is 50%), adding 4.5g of oxalic acid aqueous solution, opening steam to slowly heat up to 60 ℃, then closing steam to keep the temperature for 2 hours, adding 40.5g of residual oxalic acid aqueous solution into the kettle, controlling the reaction system to slowly heat up to 90 ℃ within 30040 minutes, keeping the temperature for 2.5 hours, adding 450g of deionized water when the free formaldehyde content of the upper water is detected to be less than 10000ppm, stirring for 30 minutes, standing for 40 minutes after stirring is finished, pumping 450g of layered upper water, carrying out normal pressure distillation and dehydration, detecting the softening point of resin to be less than 1000ppm, and adding 60% methanol of the total amount of polycondensation resin for dilution after the index is qualified.
(2) Adding 600g of phenol and 5000g of formaldehyde solution (the mass fraction of solute is 37%) and 900g of melamine into a reaction kettle, and adding ammonia water to adjust the pH value of the solution to 507; heating the reaction system to 66072 ℃, stopping heating, naturally heating to 60 ℃ and preserving heat for reaction for 1 hour; detecting that the central control viscosity is 30035mPa.s/25 ℃, and if the temperature is not up to the requirement, continuing to keep the temperature, quickly cooling to 50 ℃ until the viscosity reaches the standard, dehydrating under a vacuum state, ending the dehydration when the central control viscosity is 60070mPa.s/25 ℃, and continuing to cool to below 40 ℃ for standby.
(3) Adding 500g of the synthetic novolac resin in the step (1), 500g of the synthetic nitrogenous novolac resin in the step (2) and 100g of the organosiloxane into a reaction kettle, adding an oxalic acid aqueous solution, adjusting the pH value to 507, heating to 950100 ℃, stirring, cooling, and adding 250g of methanol for dissolution to obtain the modified phenolic resin.
Example 2: preparation of modified phenolic resin
(1) Adding 1500g of bisphenol A and 900g of acetaldehyde solution into a reaction kettle, adding 45g of benzoic acid water (the mass fraction of solute is 60%) solution, adding 4.5g of benzoic acid solution, opening steam to slowly heat up to 60 ℃, then closing steam and preserving heat for 2 hours, adding 40.5g of residual benzoic acid water solution into the kettle, controlling the reaction system to slowly heat up to 90 ℃ within 30040 minutes, preserving heat for 2.5 hours, adding 450g of deionized water when the free aldehyde of upper water is detected to be less than 10000ppm, stirring for 30 minutes, standing for 40 minutes after stirring is finished, pumping 450g of layered upper water, carrying out normal pressure distillation and dehydration, detecting the softening point of resin to 76092 ℃, and adding 60% butanone of total amount of polycondensation resin for dilution for later use after the index is qualified.
(2) Adding 900g of bisphenol A, 5000g of acetaldehyde and 900g of urea into a reaction kettle, and adding ammonia water to adjust the pH value of the solution to 507; heating the reaction system to 66072 ℃, stopping heating, naturally heating to 60 ℃ and preserving heat for reaction for 1 hour; detecting that the central control viscosity is 30035mPa.s/25 ℃, and if the temperature is not up to the requirement, continuing to keep the temperature, quickly cooling to 50 ℃ until the viscosity reaches the standard, dehydrating under a vacuum state, ending the dehydration when the central control viscosity is 60070mPa.s/25 ℃, and continuing to cool to below 40 ℃ for standby.
(3) 600g of the synthetic novolac resin in the step (1), 400g of the synthetic nitrogenous novolac resin in the step (2) and 130g of the organosiloxane are taken, added into a reaction kettle, oxalic acid aqueous solution is added, the pH value is regulated to 507, heating is carried out to 950100 ℃, stirring is finished, cooling is carried out, and 250g of butanone is added for dissolution, thus obtaining the modified novolac resin.
Example 3
An EMC package material was prepared using the modified phenolic resin prepared in example 1 as a curing agent, wherein the EMC package material components included: 10% of epoxy resin, 5% of modified phenolic resin prepared in example 1, 0.5% of curing accelerator, 60% of filler, 0.5% of coupling agent, 1% of flame retardant, 0.5% of colorant, 2% of stress absorber and 0.5% of bonding aid.
Comparative example 1
The EMC encapsulating material composition includes: 10% of epoxy resin, 5% of phosphorus-containing phenolic resin, 0.5% of curing accelerator, 60% of filler, 0.5% of coupling agent, 1% of flame retardant, 0.5% of colorant, 2% of stress absorber and 0.5% of bonding aid.
Comparative example 2
The EMC encapsulating material composition includes: 10% of epoxy resin, 5% of nitrogenous phenolic resin, 0.5% of curing accelerator, 60% of filler, 0.5% of coupling agent, 1% of flame retardant, 0.5% of colorant, 2% of stress absorber and 0.5% of bonding aid.
Experimental example 1
The EMC package materials prepared in example 3, comparative example 1 and comparative example 2 were prepared, respectively, and the performance of the EMC package materials prepared thereof was tested, and the test results are shown in table 1.
TABLE 1
From the detection results of various performances in table 1, it can be seen that the EMC packaging material prepared from the modified phenolic resin provided by the invention has excellent heat resistance, electrical insulation property and mechanical property, and the glass transition temperature is greatly improved, so that the modified phenolic resin provided by the invention can be used as a curing agent in the technical field of electrical packaging, and the electromagnetic shielding effect and stability of the material are improved.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a modified phenolic resin, which is characterized by comprising the following steps:
(1) Adding an acidic aqueous solution into a phenolic substance and an aldehyde substance, heating a reaction system to 70-100 ℃ to react for 5-6 hours, adding deionized water when detecting that free aldehyde in an upper aqueous solution meets a set standard, stirring, standing after stirring is completed, and removing solvent water to obtain the novolac resin;
(2) Adding alkaline aqueous solution into phenolic substances, aldehyde substances and nitrogen-containing compounds to adjust the pH value of the solution to 5-7, heating the reaction system to 65-85 ℃ for reaction for 1-2 h, cooling to 45-60 ℃ when the detected central control viscosity meets the set standard, and dehydrating to obtain the nitrogen-containing phenolic resin;
(3) Mixing the linear phenolic resin prepared in the step (1), the nitrogenous phenolic resin prepared in the step (2) and the organic siloxane, adding a weak acid aqueous solution, adjusting the pH value to be 5-7, heating the reaction system to 95-100 ℃ for stirring, and adding a solvent for dissolving after the stirring is completed, thus obtaining the modified phenolic resin.
2. The method of producing a modified phenolic resin as claimed in claim 1, wherein in the step (1) and the step (2), the phenolic substance comprises one or more of phenol, bisphenol a, bisphenol F, ortho-phenol, meta-cresol, para-cresol, or para-diphenol;
or, in the step (1) and the step (2), the aldehyde substance comprises one or more of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde or butyraldehyde.
3. The method for producing a modified phenolic resin as claimed in claim 1, wherein in the step (1), the mass ratio of the phenolic substance to the aldehyde substance in the step (1) is 1.5: (0.8-1);
or, the mass of the acidic aqueous solution is 2-4% of the total mass of the phenolic substances, preferably 3%;
alternatively, the reaction process comprises: firstly, adding 10% of the total mass of the acidic aqueous solution, heating the reaction system to 80 ℃, then preserving heat for 2 hours, adding the rest acidic aqueous solution, controlling the reaction system to slowly heat up to 90 ℃ within 30-40 minutes, and preserving heat for 2.5 hours.
4. The method for producing a modified phenolic resin as claimed in claim 1, wherein in the step (1), the set standard is that the free aldehyde in the upper aqueous solution is less than 10000ppm;
or, stirring for 25-40 min, preferably 30min after adding deionized water;
or, the time for standing after the completion of the stirring is 30 to 50 minutes, preferably 40 minutes.
5. The method for producing a modified phenolic resin according to claim 1, wherein in the step (2), the solute in the alkaline aqueous solution is aqueous ammonia or triethylamine;
or, the nitrogen-containing compound is one of urea or melamine;
or, in the step (2), the mass ratio of the phenolic substance to the aldehyde substance to the nitrogen-containing compound is (0.7 to 0.9): 5: (0.8-1.4).
6. The method for preparing a modified phenolic resin as claimed in claim 1, wherein in the step (2), the reaction process comprises: heating the reaction system to 68-72 ℃, stopping heating, naturally heating to 80 ℃ and preserving heat for reaction for 1 hour;
or, in the step (2), the set criteria are: the viscosity is controlled to be 30-35 mPa.s/25 ℃;
or, in the step (2), when the temperature is reduced to 50 ℃, dehydration is carried out, the medium-control viscosity is 60-70 mPa.s/25 ℃, and the dehydration is finished.
7. The method for producing a modified phenolic resin according to claim 1, wherein in the step (3), the mass ratio of the novolac resin produced in the step (1) to the nitrogen-containing phenolic resin and the organosiloxane produced in the step (2) is 50 to 60:40 to 50:10 to 15.
8. The method of claim 1, wherein in the step (3), the solvent in the step (3) is one or two of methanol, acetone and butanone.
9. A modified phenolic resin produced by the method for producing a modified phenolic resin according to any one of claims 1 to 8.
10. Use of the modified phenolic resin of claim 9 as a curing agent in an electrical packaging material.
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| CN202311364579.5A CN117510770A (en) | 2023-10-20 | 2023-10-20 | Modified phenolic resin and preparation method and application thereof |
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| CN202311364579.5A CN117510770A (en) | 2023-10-20 | 2023-10-20 | Modified phenolic resin and preparation method and application thereof |
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