CN115449211A - Flexible corrosion-resistant PPO resin-based copper-clad plate and preparation method thereof - Google Patents
Flexible corrosion-resistant PPO resin-based copper-clad plate and preparation method thereof Download PDFInfo
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- CN115449211A CN115449211A CN202211110934.1A CN202211110934A CN115449211A CN 115449211 A CN115449211 A CN 115449211A CN 202211110934 A CN202211110934 A CN 202211110934A CN 115449211 A CN115449211 A CN 115449211A
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- resin
- polyphenyl ether
- ether
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- based copper
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- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 239000011347 resin Substances 0.000 title claims abstract description 67
- 230000007797 corrosion Effects 0.000 title claims abstract description 30
- 238000005260 corrosion Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 51
- 239000003822 epoxy resin Substances 0.000 claims abstract description 39
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 39
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 229920013638 modified polyphenyl ether Polymers 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 58
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 51
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 229920001955 polyphenylene ether Polymers 0.000 claims description 47
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 40
- 238000001291 vacuum drying Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 17
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 10
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 8
- -1 N-aminoethyl-3-aminopropyl methyl siloxane Chemical class 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 claims description 5
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 5
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 5
- 229910018557 Si O Inorganic materials 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 229910000077 silane Inorganic materials 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 238000002791 soaking Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000010125 resin casting Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- XXYNZSATHOXXBJ-UHFFFAOYSA-N 4-hydroxyisoindole-1,3-dione Chemical compound OC1=CC=CC2=C1C(=O)NC2=O XXYNZSATHOXXBJ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/752—Corrosion inhibitor
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a flexible corrosion-resistant PPO resin-based copper-clad plate and a preparation method thereof; the modified epoxy resin and the modified polyphenyl ether are blended to modify the polyphenyl ether, so that the flexible corrosion-resistant polyphenyl ether resin is prepared. On one hand, the supplement of polar groups such as ether bonds in the polyphenyl ether solves the problems that the bonding capability with the copper-clad plate is reduced and the adhesive force is reduced due to the introduction of epoxy silane. On the other hand, the addition of the epoxy resin reduces the permeability of liquid in the environment to the base material, and the ether bond-containing group on the polyphenyl ether side group enhances the synergistic effect of the polyphenyl ether and the phenyl in the epoxy resin to enhance the compatibility, so that the cross-linked network structure is compact and stable, the corrosion of moisture and oxygen to the substrate is reduced, and the corrosion resistance of the polyphenyl ether is greatly improved. Due to the introduction of Si-O in the modified epoxy resin in the modified polyphenyl ether, the flexibility of the polyphenyl ether is enhanced, and the impact resistance is improved.
Description
Technical Field
The invention relates to the technical field of PPO resin-based copper-clad plates, in particular to a flexible corrosion-resistant PPO resin-based copper-clad plate and a preparation method thereof.
Background
With the continuous development of social information technology, the demand for high-speed and high-frequency copper-clad plates is rapidly increased, and people have higher requirements for the performance of the copper-clad plates. The matrix resin of the existing copper-clad plate mainly comprises epoxy resin, has the defects of poor heat resistance, high dielectric constant and high dielectric loss, and cannot meet the requirements of people.
However, in the actual application and development process, the polyphenylene ether resin is often high in molecular weight, so that the viscosity of the polyphenylene ether resin in a molten state is too high, the polyphenylene ether resin is difficult to process and is not suitable for copper clad laminate development, and the polyphenylene ether resin with low molecular weight has the problem of weak crosslinking capability. The main chain contains rigid benzene rings, so that the shock resistance of the copper clad laminate is poor, and the polyphenyl ether is thermoplastic resin and has no practical value without modification in the field of copper clad laminates.
Therefore, the invention has important significance in preparing the flexible corrosion-resistant PPO resin-based copper-clad plate.
Disclosure of Invention
The invention aims to provide a flexible corrosion-resistant PPO resin-based copper-clad plate and a preparation method thereof, and aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a flexible corrosion-resistant PPO resin-based copper-clad plate comprises the following steps:
s1: dissolving hydroxyl-terminated polyphenyl ether in tetrahydrofuran solution, adding N-bromosuccinimide and benzoyl peroxide, and heating to react in a nitrogen atmosphere; cooling, washing and vacuum drying to obtain polyphenyl ether A;
s2: adding polyphenyl ether A and 3a,4,7 a-tetrahydro-1H-4, 7-epoxy isoindole-1, 3 (2H) -diketone into tetrahydrofuran, adding potassium carbonate, and heating to react under the atmosphere of nitrogen gas; cooling, washing and vacuum drying to obtain polyphenyl ether B;
s3: adding polyphenyl ether B, epoxy chloropropane and tetrabutylammonium bromide into a reaction container, dropwise adding a sodium hydroxide solution under the atmosphere of nitrogen gas, heating and stirring; cooling, filtering, washing and vacuum drying to obtain polyphenyl ether C;
s4: dissolving polyphenyl ether C in tetrahydrofuran, adding a mixed acetone solution of modified epoxy resin and 4,4' -diaminodiphenyl sulfone, ultrasonically homogenizing, and drying in vacuum to obtain modified polyphenyl ether resin; and adding the modified polyphenylene oxide resin into a copper clad laminate mold, and curing to obtain the flexible corrosion-resistant PPO resin-based copper clad laminate.
Further, in the step S1, the hydroxyl-terminated polyphenylene ether is prepared as follows:
dissolving 2, 6-dimethylphenol and tetramethyl bisphenol A in toluene, adding cuprous chloride and di-n-butylamine, introducing oxygen, and carrying out primary heating reaction to obtain a polymer solution; adding a sodium nitrilotriacetate solution, and carrying out secondary heating reaction; centrifuging, performing rotary evaporation, filtering, washing and vacuum drying to obtain hydroxyl-terminated polyphenyl ether;
wherein, 2, 6-dimethylphenol: the mass ratio of the tetramethyl bisphenol A is 11:1; the primary heating reaction temperature is 40-45 ℃, and the primary heating reaction time is 3 hours; the mass of the sodium nitrilotriacetate solution is 10 percent of the mass of the polymer solution, the secondary heating reaction temperature is 65-70 ℃, the secondary heating reaction time is 1h, and the vacuum drying temperature is 80 ℃.
Further, in the step S1, the hydroxyl-terminated polyphenylene ether: n-bromosuccinimide: the mass ratio of the benzoyl peroxide is 16:7:1; the heating reaction temperature is 75-80 ℃, and the heating reaction time is 2-2.5 h.
Further, in the step S2, polyphenylene ether a:3a,4,7 a-tetrahydro-1H-4, 7-oxisoindole-1, 3 (2H) -dione: the mass ratio of the potassium carbonate is 4:2:1; the heating reaction temperature is 45-50 ℃, and the heating reaction time is 8h.
Further, in step S3, polyphenylene ether B: epoxy chloropropane: tetrabutylammonium bromide: the mass ratio of the sodium hydroxide aqueous solution is 8:90:1:4, the concentration of the sodium hydroxide aqueous solution is 40 percent; the heating and stirring temperature is 75-80 ℃, the heating and stirring time is 3-4 h, and the vacuum drying temperature is 70 ℃.
Further, in the step S4, the modified epoxy resin is prepared as follows:
adding phenyl trimethoxy silane, dimethyl dimethoxy silane, methanol, water and hydrochloric acid into a reaction container, and heating for reaction to obtain siloxane A; adding 3-glycidyl ether oxypropyldimethoxysilane, refluxing for the first time, adding water and hydrochloric acid, and refluxing for the second time to obtain a crude product; adding trifluoromethanesulfonic acid, and carrying out secondary heating reaction to obtain a modifier; adding the epoxy resin and the modifier into xylene, stirring uniformly, adding N-aminoethyl-3-aminopropyl methyl siloxane, and stirring uniformly to obtain the modified epoxy resin.
Further, the phenyltrimethoxysilane: dimethyl dimethoxy silane: methanol: water: the mass ratio of the 3-glycidyl ether oxypropyldimethoxysilane to the glycidyl ether oxypropyldimethoxysilane is 7:2:4:1:1.5, the heating reaction temperature is 70-80 ℃, the heating reaction time is 4h, the primary reflux time is 0.5h, and the secondary reflux time is 2.5h; the adding amount of the trifluoromethanesulfonic acid is 40ppm of the mass of the crude product, the secondary heating reaction temperature is 130 ℃, and the reaction time is 5-7 h; epoxy resin: modifying agent: the mass ratio of the N-aminoethyl-3-aminopropyl methyl siloxane to the N-aminopropyl methyl siloxane is 11:5:1.
further, in step S4, polyphenylene ether C: modified epoxy resin: the mass ratio of the 4,4' -diamino diphenyl sulfone is (7-8.5): (1.5-3): (0.5-1.1) and the vacuum drying temperature is 50 ℃.
Compared with the prior art, the invention has the following beneficial effects: the invention prepares low molecular weight double-end hydroxyl polyphenylene oxide; on one hand, a group containing ether bond is introduced on the side group, so that the polyphenyl ether is compatible with the epoxy resin to form a complete and stable cross-linked network structure, the compatibility of the polyphenyl ether and the epoxy resin is improved, and the adhesive force is enhanced; on the other hand, the double-end hydroxyl groups of the polyphenylene ether are modified into double-end epoxy groups, so that the curing capability of the polyphenylene ether is enhanced while the dielectric property of the polyphenylene ether is kept.
According to the invention, epoxy siloxane is introduced into an epoxy resin system, on one hand, the epoxy value of the system in the modification process is maintained, and the consumption of the epoxy group of the epoxy resin is counteracted, and on the other hand, the compatibility of the epoxy resin and polyphenyl ether is greatly improved by phenyl and other groups in the modifier. Due to the introduction of the organic silicon, the Si-O bond energy is high, so that the impact resistance of the epoxy resin is greatly improved.
The invention relates to a flexible corrosion-resistant polyphenyl ether resin prepared by modifying polyphenyl ether in a mode of blending modified epoxy resin and polyphenyl ether. On one hand, the supplement of polar groups such as ether bonds in the polyphenyl ether solves the problems that the bonding capability with the copper-clad plate is reduced and the adhesive force is reduced due to the introduction of epoxy silane. On the other hand, the addition of the epoxy resin reduces the permeability of liquid in the environment to the base material, and the ether bond group on the polyphenyl ether side group enhances the synergistic effect of the polyphenyl ether and phenyl in the epoxy resin to enhance the compatibility, so that the cross-linked network structure is compact and stable, the corrosion of moisture and oxygen to a substrate is reduced, and the corrosion resistance of the polyphenyl ether is greatly improved. Due to the introduction of Si-O in the modified epoxy resin in the modified polyphenyl ether, the flexibility of the polyphenyl ether is enhanced, and the impact resistance is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, hydroxyl-terminated polyphenylene ethers were prepared as follows:
dissolving 11g of 2, 6-dimethylphenol and 1g of tetramethyl bisphenol A in 30mL of toluene, adding 0.1g of cuprous chloride and 30g of di-n-butylamine, introducing oxygen, heating to 45 ℃, and reacting for 3 hours to obtain a polymer solution; 2g of sodium nitrilotriacetate solution (with a solids content of 25%) are added to 18g of the polymer solution and the mixture is heated to 70 ℃ for reaction for 1h; centrifuging to remove water phase, performing rotary evaporation until the solid content is 40%, filtering, washing with methanol for 3 times, and vacuum drying at 80 deg.C for 24 hr to obtain hydroxyl-terminated polyphenylene ether;
the modified epoxy resin is prepared by the following method:
adding 14g of phenyltrimethoxysilane, 4g of dimethyldimethoxysilane, 8g of methanol, 2g of water and 0.1mL of 25% hydrochloric acid into a reaction vessel, and heating to 80 ℃ for reaction for 4 hours to obtain siloxane A; adding 3g of 3-glycidyl ether oxypropyldimethoxysilane, refluxing for 0.5h, adding 0.5g of water and 0.05mL of hydrochloric acid, and refluxing for 2.5h to obtain a crude product; adding 0.4mg of trifluoromethanesulfonic acid into 10g of the crude product, heating to 130 ℃ and reacting for 7h to obtain a modifier; adding 11g of epoxy resin and 5g of modifier into 50mL of dimethylbenzene, uniformly stirring, adding 1g of N-aminoethyl-3-aminopropyl methyl siloxane, and uniformly stirring to obtain modified epoxy resin;
n-bromosuccinimide is supplied by Sahn chemical technology (Shanghai) Inc.;
3a,4,7 a-tetrahydro-1H-4, 7-oxidoisoindole-1, 3 (2H) -dione (FHMI) was prepared from the literature "Synthesis and characterization of polyphenylene ethers containing maleimide groups in their pendant groups".
Example 1
S1: dissolving 16g of hydroxyl-terminated polyphenyl ether in 50mL of tetrahydrofuran solution, adding 7g of N-bromosuccinimide and 1g of benzoyl peroxide, and heating to 80 ℃ to react for 2h in the atmosphere of nitrogen gas; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene oxide A;
s2: adding 8g of polyphenylene oxide A and 4g of 3a,4,7 a-tetrahydro-1H-4, 7-epoxy isoindole-1, 3 (2H) -diketone into 30mL of tetrahydrofuran, adding 2g of potassium carbonate, and heating to 50 ℃ under the atmosphere of nitrogen gas to react for 8 hours; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene oxide B;
s3: adding 8g of polyphenyl ether B, 90g of epoxy chloropropane and 1g of tetrabutylammonium bromide into a reaction container, dropwise adding 4g of 40% sodium hydroxide solution under the atmosphere of nitrogen gas, heating to 80 ℃, and stirring for 4 hours; cooling, filtering, washing, and vacuum drying at 70 deg.C until completely dried to obtain polyphenylene ether C;
s4: dissolving 7g of polyphenyl ether C in 100mL of tetrahydrofuran, adding a mixed acetone solution of 1.5g of modified epoxy resin and 0.5g of 4,4' -diaminodiphenyl sulfone, wherein the acetone solvent is 100mL, ultrasonically homogenizing for 30min, and carrying out vacuum drying at 50 ℃ for 24h to obtain modified polyphenyl ether resin; adding the modified polyphenylene oxide resin into a copper clad laminate mold, and placing the mold into a flat press for curing, wherein the curing procedures are 10min at 170 ℃, 10min at 180 ℃,190 ℃ and 30min at 220 ℃, so as to obtain the flexible corrosion-resistant PPO resin-based copper clad laminate.
And (3) testing: curing the modified polyphenylene ether resin, soaking the cured modified polyphenylene ether resin in a 3.5wt% sodium chloride solution for 168 hours, and measuring the impedance performance of the coating in the middle soaking period;
after the modified polyphenylene ether resin is cured, the tensile strength, the elongation at break and the impact strength at room temperature are measured according to GB/T2567-2021 resin casting body performance test method.
Example 2
S1: dissolving 16g of hydroxyl-terminated polyphenyl ether in 50mL of tetrahydrofuran solution, adding 7g of N-bromosuccinimide and 1g of benzoyl peroxide, and heating to 80 ℃ to react for 2 hours in the nitrogen atmosphere; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene oxide A;
s2: adding 8g of polyphenylene oxide A and 4g of 3a,4,7 a-tetrahydro-1H-4, 7-epoxy isoindole-1, 3 (2H) -diketone into 30mL of tetrahydrofuran, adding 2g of potassium carbonate, and heating to 50 ℃ under the atmosphere of nitrogen gas to react for 8 hours; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene ether B;
s3: adding 8g of polyphenyl ether B, 90g of epoxy chloropropane and 1g of tetrabutylammonium bromide into a reaction container, dropwise adding 4g of 40% sodium hydroxide solution under the atmosphere of nitrogen gas, heating to 80 ℃, and stirring for 4 hours; cooling, filtering, washing, and vacuum drying at 70 ℃ until completely drying to obtain polyphenylene ether C;
s4: dissolving 8g of polyphenylene oxide C in 100mL of tetrahydrofuran, adding a mixed acetone solution of 2.5g of modified epoxy resin and 0.8g of 4,4' -diaminodiphenyl sulfone, wherein the acetone solvent is 100mL, ultrasonically homogenizing for 30min, and carrying out vacuum drying at 50 ℃ for 24h to obtain modified polyphenylene oxide resin; adding the modified polyphenylene oxide resin into a copper clad laminate mold, and placing the mold into a flat press for curing, wherein the curing procedures are 10min at 170 ℃, 10min at 180 ℃, min at 190 ℃ and 30min at 220 ℃ to obtain the flexible corrosion-resistant PPO resin-based copper clad laminate.
And (3) testing: curing the modified polyphenylene ether resin, soaking the cured modified polyphenylene ether resin in a 3.5wt% sodium chloride solution for 168 hours, and measuring the impedance performance of the coating in the middle soaking period;
after the modified polyphenylene ether resin is cured, the tensile strength, the elongation at break and the impact strength at room temperature are measured according to GB/T2567-2021 resin casting body performance test method.
Example 3
S1: dissolving 16g of hydroxyl-terminated polyphenyl ether in 50mL of tetrahydrofuran solution, adding 7g of N-bromosuccinimide and 1g of benzoyl peroxide, and heating to 80 ℃ to react for 2 hours in the nitrogen atmosphere; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene oxide A;
s2: adding 8g of polyphenylene oxide A and 4g of 3a,4,7 a-tetrahydro-1H-4, 7-epoxy isoindole-1, 3 (2H) -diketone into 30mL of tetrahydrofuran, adding 2g of potassium carbonate, and heating to 50 ℃ under the atmosphere of nitrogen gas to react for 8 hours; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene oxide B;
s3: adding 8g of polyphenyl ether B, 90g of epoxy chloropropane and 1g of tetrabutylammonium bromide into a reaction container, dropwise adding 4g of 40% sodium hydroxide solution under the atmosphere of nitrogen gas, heating to 80 ℃, and stirring for 4 hours; cooling, filtering, washing, and vacuum drying at 70 deg.C until completely dried to obtain polyphenylene ether C;
s4: dissolving 8.5g of polyphenyl ether C in 100mL of tetrahydrofuran, adding a mixed acetone solution of 3g of modified epoxy resin and 1.1g of 4,4' -diaminodiphenyl sulfone, wherein the acetone solvent is 100mL, carrying out ultrasonic homogenization for 30min, and carrying out vacuum drying at 50 ℃ for 24h to obtain modified polyphenyl ether resin; adding the modified polyphenylene oxide resin into a copper clad laminate mold, and placing the mold into a flat press for curing, wherein the curing procedures are 10min at 170 ℃, 10min at 180 ℃,190 ℃ and 30min at 220 ℃, so as to obtain the flexible corrosion-resistant PPO resin-based copper clad laminate.
And (3) testing: curing the modified polyphenylene oxide resin, soaking in 3.5wt% sodium chloride solution for 168h, and measuring the impedance performance of the coating in the middle soaking period;
after the modified polyphenylene ether resin is cured, the tensile strength, the elongation at break and the impact strength at room temperature are measured according to GB/T2567-2021 resin casting body performance test method.
Comparative example 1 (unmodified epoxy resin)
S1: dissolving 16g of hydroxyl-terminated polyphenyl ether in 50mL of tetrahydrofuran solution, adding 7g of N-bromosuccinimide and 1g of benzoyl peroxide, and heating to 80 ℃ to react for 2h in the atmosphere of nitrogen gas; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene oxide A;
s2: adding 8g of polyphenylene oxide A and 4g of 3a,4,7 a-tetrahydro-1H-4, 7-epoxy isoindole-1, 3 (2H) -diketone into 30mL of tetrahydrofuran, adding 2g of potassium carbonate, and heating to 50 ℃ under the atmosphere of nitrogen gas to react for 8 hours; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene oxide B;
s3: adding 8g of polyphenyl ether B, 90g of epoxy chloropropane and 1g of tetrabutylammonium bromide into a reaction container, dropwise adding 4g of 40% sodium hydroxide solution under the atmosphere of nitrogen gas, heating to 80 ℃, and stirring for 4 hours; cooling, filtering, washing, and vacuum drying at 70 deg.C until completely dried to obtain polyphenylene ether C;
s4: dissolving 8.5g of polyphenyl ether C in 100mL of tetrahydrofuran, adding a mixed acetone solution of 3g of epoxy resin and 1.1g of 4,4' -diaminodiphenyl sulfone, wherein the acetone solvent is 100mL, carrying out ultrasonic homogenization for 30min, and carrying out vacuum drying for 24h at 50 ℃ to obtain modified polyphenyl ether resin; adding the modified polyphenylene oxide resin into a copper clad laminate mold, and placing the mold into a flat press for curing, wherein the curing procedures are 10min at 170 ℃, 10min at 180 ℃,190 ℃ and 30min at 220 ℃, so as to obtain the flexible corrosion-resistant PPO resin-based copper clad laminate.
And (3) testing: curing the modified polyphenylene oxide resin, soaking in 3.5wt% sodium chloride solution for 168h, and measuring the impedance performance of the coating in the middle soaking period;
after the modified polyphenylene ether resin is cured, the tensile strength, the elongation at break and the impact strength at room temperature are measured according to GB/T2567-2021 resin casting body performance test method.
Comparative example 2 (polyphenylene ether non-terminal epoxy modified)
S1: dissolving 16g of hydroxyl-terminated polyphenyl ether in 50mL of tetrahydrofuran solution, adding 7g of N-bromosuccinimide and 1g of benzoyl peroxide, and heating to 80 ℃ to react for 2h in the atmosphere of nitrogen gas; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene oxide A;
s2: adding 8g of polyphenylene oxide A and 4g of 3a,4,7 a-tetrahydro-1H-4, 7-epoxy isoindole-1, 3 (2H) -diketone into 30mL of tetrahydrofuran, adding 2g of potassium carbonate, and heating to 50 ℃ under the atmosphere of nitrogen gas to react for 8 hours; cooling, washing with methanol for 3 times, and vacuum drying to obtain polyphenylene oxide B;
s3: dissolving 8.5g of polyphenyl ether B in 100mL of tetrahydrofuran, adding a mixed acetone solution of 3g of modified epoxy resin and 1.1g of 4,4' -diaminodiphenyl sulfone, wherein the acetone solvent is 100mL, carrying out ultrasonic homogenization for 30min, and carrying out vacuum drying at 50 ℃ for 24h to obtain modified polyphenyl ether resin; adding the modified polyphenylene oxide resin into a copper clad laminate mold, and placing the mold into a flat press for curing, wherein the curing procedures are 10min at 170 ℃, 10min at 180 ℃,190 ℃ and 30min at 220 ℃, so as to obtain the flexible corrosion-resistant PPO resin-based copper clad laminate.
And (3) testing: curing the modified polyphenylene ether resin, soaking the cured modified polyphenylene ether resin in a 3.5wt% sodium chloride solution for 168 hours, and measuring the impedance performance of the coating in the middle soaking period;
after the modified polyphenylene ether resin is cured, the tensile strength, the elongation at break and the impact strength at room temperature are measured according to GB/T2567-2021 resin casting body performance test method.
Comparative example 3 (polyphenylene ether modified with epoxy groups bonded to non-pendant groups)
S1: adding 8g of hydroxyl-terminated polyphenyl ether B, 90g of epoxy chloropropane and 1g of tetrabutylammonium bromide into a reaction container, dropwise adding 4g of 40% sodium hydroxide solution under the atmosphere of nitrogen gas, heating to 80 ℃, and stirring for 4 hours; cooling, filtering, washing, and vacuum drying at 70 deg.C until completely dried to obtain polyphenylene ether C;
s2: dissolving 8.5g of polyphenyl ether C in 100mL of tetrahydrofuran, adding a mixed acetone solution of 3g of modified epoxy resin and 1.1g4,4' -diaminodiphenyl sulfone, wherein the acetone solvent is 100mL, ultrasonically homogenizing for 30min, and drying in vacuum at 50 ℃ for 24h to obtain modified polyphenyl ether resin; adding the modified polyphenylene oxide resin into a copper clad laminate mold, and placing the mold into a flat press for curing, wherein the curing procedures are 10min at 170 ℃, 10min at 180 ℃,190 ℃ and 30min at 220 ℃, so as to obtain the flexible corrosion-resistant PPO resin-based copper clad laminate.
And (3) testing: curing the modified polyphenylene ether resin, soaking the cured modified polyphenylene ether resin in a 3.5wt% sodium chloride solution for 168 hours, and measuring the impedance performance of the coating in the middle soaking period;
after the modified polyphenylene ether resin is cured, the tensile strength, the elongation at break and the impact strength at room temperature are measured according to GB/T2567-2021 resin casting body performance test method.
As can be seen from examples 1 to 3, when polyphenylene ether C: modified epoxy resin: the mass ratio of 4,4' -diamino diphenyl sulfone is 8.5:3:1.1, the dielectric property and the mechanical property are best.
In comparative example 1, epoxy resin was not modified with epoxysiloxane, so that the modified polyphenylene ether resin lacked Si-O groups, the compatibility decreased, and the mechanical properties of the polyphenylene ether resin decreased.
In comparative example 2, polyphenylene ether was not subjected to epoxy group-terminating modification, resulting in a decrease in the curing ability of the system, and non-uniform curing during curing, resulting in a decrease in dielectric properties and mechanical properties.
In comparative example 3, the polyphenylene ether side group was not grafted with a maleimide group, resulting in a decrease in the crosslinking ability of the low molecular weight polyphenylene ether, and the crosslinked network was unstable, resulting in a decrease in mechanical properties.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a flexible corrosion-resistant PPO resin-based copper-clad plate is characterized by comprising the following steps: the method comprises the following steps:
s1: dissolving hydroxyl-terminated polyphenyl ether in a tetrahydrofuran solution, adding N-bromosuccinimide and benzoyl peroxide, and heating to react in a nitrogen atmosphere; cooling, washing and vacuum drying to obtain polyphenyl ether A;
s2: adding polyphenyl ether A and 3a,4,7 a-tetrahydro-1H-4, 7-epoxy isoindole-1, 3 (2H) -diketone into tetrahydrofuran, adding potassium carbonate, and heating to react under the atmosphere of nitrogen gas; cooling, washing and vacuum drying to obtain polyphenyl ether B;
s3: adding polyphenyl ether B, epoxy chloropropane and tetrabutylammonium bromide into a reaction container, dropwise adding a sodium hydroxide solution under the atmosphere of nitrogen gas, heating and stirring; cooling, filtering, washing and vacuum drying to obtain polyphenyl ether C;
s4: dissolving polyphenyl ether C in tetrahydrofuran, adding a mixed acetone solution of modified epoxy resin and 4,4' -diaminodiphenyl sulfone, ultrasonically homogenizing, and drying in vacuum to obtain modified polyphenyl ether resin; and adding the modified polyphenylene oxide resin into a copper clad laminate mold, and curing to obtain the flexible corrosion-resistant PPO resin-based copper clad laminate.
2. The preparation method of the flexible corrosion-resistant PPO resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the step S1, the hydroxyl-terminated polyphenyl ether is prepared by the following method:
dissolving 2, 6-dimethylphenol and tetramethyl bisphenol A in toluene, adding cuprous chloride and di-n-butylamine, introducing oxygen, and carrying out primary heating reaction to obtain a polymer solution; adding a sodium nitrilotriacetate solution, and carrying out secondary heating reaction; centrifuging, performing rotary evaporation, filtering, washing and vacuum drying to obtain hydroxyl-terminated polyphenyl ether;
wherein, 2, 6-dimethylphenol: the mass ratio of the tetramethyl bisphenol A is 11:1; the primary heating reaction temperature is 40-45 ℃, and the primary heating reaction time is 3 hours; the mass of the sodium nitrilotriacetate solution is 10 percent of the mass of the polymer solution, the secondary heating reaction temperature is 65-70 ℃, the secondary heating reaction time is 1h, and the vacuum drying temperature is 80 ℃.
3. The preparation method of the flexible corrosion-resistant PPO resin-based copper-clad plate according to claim 1, which is characterized in that: in step S1, hydroxyl-terminated polyphenylene ether: n-bromosuccinimide: the mass ratio of the benzoyl peroxide is 16:7:1; the heating reaction temperature is 75-80 ℃, and the heating reaction time is 2-2.5 h.
4. The preparation method of the flexible corrosion-resistant PPO resin-based copper-clad plate according to claim 1, which is characterized in that: in step S2, polyphenylene ether A:3a,4,7 a-tetrahydro-1H-4, 7-oxisoindole-1, 3 (2H) -dione: the mass ratio of the potassium carbonate is 4:2:1; the heating reaction temperature is 45-50 ℃, and the heating reaction time is 8h.
5. The preparation method of the flexible corrosion-resistant PPO resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in step S3, polyphenylene ether B: epichlorohydrin: tetrabutylammonium bromide: the mass ratio of the sodium hydroxide aqueous solution is 8:90:1:4, the concentration of the sodium hydroxide aqueous solution is 40 percent; the heating and stirring temperature is 75-80 ℃, the heating and stirring time is 3-4 h, and the vacuum drying temperature is 70 ℃.
6. The preparation method of the flexible corrosion-resistant PPO resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in step S4, the modified epoxy resin is prepared as follows:
adding phenyl trimethoxy silane, dimethyl dimethoxy silane, methanol, water and hydrochloric acid into a reaction vessel, and heating for reaction to obtain siloxane A; adding 3-glycidyl ether oxypropyldimethoxysilane, refluxing for the first time, adding water and hydrochloric acid, and refluxing for the second time to obtain a crude product; adding trifluoromethanesulfonic acid, and carrying out secondary heating reaction to obtain a modifier; adding the epoxy resin and the modifier into xylene, stirring uniformly, adding N-aminoethyl-3-aminopropyl methyl siloxane, and stirring uniformly to obtain the modified epoxy resin.
7. The preparation method of the flexible corrosion-resistant PPO resin-based copper-clad plate according to claim 6, which is characterized by comprising the following steps: phenyl trimethoxy silane: dimethyl dimethoxy silane: methanol: water: the mass ratio of the 3-glycidyl ether oxypropyldimethoxysilane is 7:2:4:1:1.5, the heating reaction temperature is 70-80 ℃, the heating reaction time is 4h, the primary reflux time is 0.5h, and the secondary reflux time is 2.5h; the adding amount of the trifluoromethanesulfonic acid is 40ppm of the mass of the crude product, the secondary heating reaction temperature is 130 ℃, and the reaction time is 5-7 h; epoxy resin: modifying agent: the mass ratio of the N-aminoethyl-3-aminopropyl methyl siloxane to the N-aminoethyl-3-aminopropyl methyl siloxane is 11:5:1.
8. the preparation method of the flexible corrosion-resistant PPO resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in step S4, polyphenylene ether C: modified epoxy resin: the mass ratio of the 4,4' -diamino diphenyl sulfone is (7-8.5): (1.5-3): (0.5-1.1) and the vacuum drying temperature is 50 ℃.
9. The PPO resin-based copper-clad plate prepared by the preparation method of the flexible corrosion-resistant PPO resin-based copper-clad plate according to any one of claims 1 to 8.
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