CN116285229B - Ceramic toughening epoxy resin for halogen-free copper-clad plate and preparation method thereof - Google Patents
Ceramic toughening epoxy resin for halogen-free copper-clad plate and preparation method thereof Download PDFInfo
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- CN116285229B CN116285229B CN202310345835.XA CN202310345835A CN116285229B CN 116285229 B CN116285229 B CN 116285229B CN 202310345835 A CN202310345835 A CN 202310345835A CN 116285229 B CN116285229 B CN 116285229B
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- epoxy resin
- boron nitride
- hexagonal boron
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- free copper
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 50
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 50
- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910052582 BN Inorganic materials 0.000 claims abstract description 86
- 239000002135 nanosheet Substances 0.000 claims abstract description 78
- 229920001690 polydopamine Polymers 0.000 claims abstract description 35
- 229920000548 poly(silane) polymer Polymers 0.000 claims abstract description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 33
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 27
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 18
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 claims description 15
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 15
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 15
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000012362 glacial acetic acid Substances 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 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 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 4
- 229960003638 dopamine Drugs 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009864 tensile test Methods 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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Ceramic Products (AREA)
Abstract
The invention relates to the field of copper-clad plates, in particular to ceramic toughening epoxy resin for a halogen-free copper-clad plate and a preparation method thereof. According to the invention, firstly, the hexagonal boron nitride nanosheets are treated by chemical means, and the peeling and modification of the hexagonal boron nitride nanosheets are realized by utilizing the characteristics of dopamine precipitation and self polymerization, so that the polydopamine-loaded hexagonal boron nitride nanosheets are obtained; and then using gamma-glycidol ether oxypropyl trimethoxy silane to carry out grafting and hyperbranched reaction on the surface of polydopamine to obtain the epoxy hyperbranched polysilane grafted hexagonal boron nitride nanosheets with three-dimensional network structures. The epoxy hyperbranched polysilane grafted hexagonal boron nitride nanosheets have better compatibility with epoxy resin, retain the advantage of high mechanical strength of boron nitride and can toughen and modify the epoxy resin. In addition, the three-dimensional reticular structure can improve a continuous and compact heat conduction network, greatly improve the heat conduction performance of the epoxy resin and meet the application requirement of the copper-clad plate.
Description
Technical Field
The invention relates to the technical field, in particular to ceramic toughening epoxy resin for a halogen-free copper-clad plate and a preparation method thereof.
Background
The continuous progress of mobile communication technology places higher demands on the performance of hardware devices. In order to achieve stable transmission and reception of electronic signals at high frequencies, precise control of various performance parameters of the circuit board is required. The copper-clad plate is used as a substrate material in a printed circuit board, is generally mixed with electronic glass fiber or other rigidity reinforcing materials by resin, and is coated with copper on one side or two sides, and the main functions of the copper-clad plate include: conductive, insulating, supporting and signal transmitting functions. At present, the copper-clad plate is developing towards high heat conduction, low dielectric loss and high peel strength.
The epoxy resin has the characteristics of small curing shrinkage, high viscosity of a cured product, good chemical corrosion resistance, excellent electrical performance and the like, and is a common copper-clad plate base material. With the updating of electronic products, the traditional epoxy resin-based copper-clad plate is difficult to meet the requirements of heat resistance, flame retardance and the like. The boron nitride ceramic material has a similar structure with graphene, has lower dielectric constant and higher thermal conductivity than the graphene, and is expected to be applied to epoxy resin modification to prepare a circuit board substrate with excellent performance. However, boron nitride is chemically stable, and has poor dispersibility after being directly blended with epoxy resin, and the performance of the final material is even degraded. Therefore, there is a need to treat boron nitride ceramic materials to improve their compatibility with epoxy resins.
Disclosure of Invention
The invention aims to provide ceramic toughening epoxy resin for a halogen-free copper-clad plate and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the ceramic toughening epoxy resin for the halogen-free copper-clad plate and the preparation method thereof comprise the following steps:
step 1: adding tris (hydroxymethyl) aminomethane into deionized water, regulating the pH to 8-8.5 by using dilute hydrochloric acid, uniformly mixing, adding dopamine hydrochloride, continuously stirring for 15-30 min, adding hexagonal boron nitride nanosheets, uniformly dispersing by ultrasonic waves, heating in a water bath, and standing for reaction to obtain polydopamine-loaded hexagonal boron nitride nanosheets;
step 2: adding polydopamine-loaded hexagonal boron nitride nanosheets into tetrahydrofuran, adding glacial acetic acid, heating in a water bath, heating, adding gamma-glycidol ether oxypropyl trimethoxy silane, refluxing, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nanosheets;
step 3: and heating bisphenol A epoxy resin, adding a curing agent, a curing accelerator, ethanol, acetone, a flame retardant, hyperbranched polysilane grafted hexagonal boron nitride nanosheets and an antioxidant, and uniformly mixing to obtain the ceramic toughening epoxy resin for the halogen-free copper-clad plate.
Further, in the step 1, the weight of each component is 0.7 to 1 part of tris (hydroxymethyl) aminomethane, 500 to 600 parts of deionized water, 1.5 to 2 parts of dopamine hydrochloride and 3 to 4 parts of hexagonal boron nitride nano-sheets.
Further, in the step 1, the ultrasonic dispersion time is 2-3 hours; the heating temperature of the water bath is 55-65 ℃; the standing reaction time is 20-30 h.
Further, in the step 2, the amount of each component is 0.5 to 0.8 part by weight of hexagonal boron nitride nano-sheet loaded with polydopamine, 8 to 10 parts by weight of tetrahydrofuran, 1 to 2 parts by weight of glacial acetic acid and 2 to 3 parts by weight of gamma-glycidoxypropyl trimethoxysilane.
In the step 2, the water bath heating temperature is 70-80 ℃; the reflux time is 25-30 h.
In step 3, the ceramic toughening epoxy resin for the halogen-free copper-clad plate comprises, by weight, 90-120 parts of bisphenol A epoxy resin, 20-30 parts of curing agent, 0.3-0.6 part of curing accelerator, 10-20 parts of ethanol, 15-20 parts of acetone, 5-15 parts of flame retardant, 20-30 parts of hyperbranched polysilane grafted hexagonal boron nitride nano-sheet and 1-2 parts of antioxidant.
Further, in the step 3, the curing agent is any one of diethylenetriamine, maleic anhydride, tetraethylenepentamine, phthalic anhydride and m-phenylenediamine; the curing accelerator is any one of 4-dimethylaminopyridine, 2-methylimidazole and 2-phenylimidazole; the antioxidant is any one of an antioxidant 1010, an antioxidant 1076, an antioxidant 168, an antioxidant 1098 and an antioxidant 264; the flame retardant is any one of tri (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, zinc borate, aluminum hydroxide, magnesium hydroxide and ammonium polyphosphate.
In step 3, the heating temperature of the bisphenol A epoxy resin is 50-60 ℃.
Compared with the prior art, the invention has the following beneficial effects: the invention uses boron nitride ceramic material with high mechanical strength and high heat conductivity coefficient to toughen and modify the epoxy. Firstly, depositing and self-polymerizing dopamine on the surface of a hexagonal boron nitride nano-sheet to form a polydopamine layer, and loading the polydopamine layer on the surface of the hexagonal boron nitride nano-sheet. After polydopamine is loaded, on one hand, the stripping of the hexagonal boron nitride nanosheets is realized, the agglomeration phenomenon generated during the blending of epoxy resin is avoided, and the uniform dispersion is facilitated; on the other hand, the polydopamine surface is provided with abundant active groups, epoxy hyperbranched polysilane grafting is carried out on the polydopamine surface, and epoxy groups are introduced, so that the compatibility of the boron nitride filler and epoxy resin can be further improved. The hyperbranched structure and the hexagonal boron nitride nanosheets form a three-dimensional network structure together, so that a continuous and compact heat conducting network is generated, the heat conducting performance of the epoxy resin is improved, and the actual production and application requirements are met.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The main materials and sources thereof in the following examples are as follows:
trimethylol aminomethane (CAS number: 77-86-1), dilute hydrochloric acid (CAS number: 7647-01-0), dopamine hydrochloride (CAS number: 62-31-7), tetrahydrofuran (CAS number: 109-99-9), glacial acetic acid (CAS number: 64-19-7), gamma-glycidoxypropyl trimethoxysilane (CAS number: 2530-83-8), ethanol (CAS number: 64-17-5), acetone (CAS number: 67-64-1) were purchased from Allatin; hexagonal boron nitride nanoplatelets (CAS number: 10043-11-5) are purchased from Tianyuan aerospace; bisphenol A epoxy resin is purchased from a new material, product number WSR 6101; maleic anhydride (CAS number: 108-31-6) was purchased from Ji Xiangteng and 4-dimethylaminopyridine (CAS number: 1122-58-3) was purchased from the requisite chemical industry, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (CAS number: 99208-50-1) and Yu Jieheng chemical industry.
Example 1:
step 1: adding 0.7g of tris (hydroxymethyl) aminomethane into 500g of deionized water, regulating the pH to 8 by using dilute hydrochloric acid, adding 1.5g of dopamine hydrochloride after uniformly mixing, continuously stirring for 15min, adding 3g of hexagonal boron nitride nano-sheets, performing ultrasonic dispersion for 2h, heating to 55 ℃ in a water bath, and standing for 20h to obtain polydopamine-loaded hexagonal boron nitride nano-sheets;
step 2: adding 0.5g of polydopamine-loaded hexagonal boron nitride nanosheets into 8g of tetrahydrofuran, adding 1g of glacial acetic acid, heating to 70 ℃ in a water bath, adding 2g of gamma-glycidol ether oxypropyl trimethoxysilane, refluxing for 25h, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nanosheets;
step 3: 90kg of bisphenol A epoxy resin is heated to 50 ℃, 20kg of maleic anhydride, 0.3kg of 4-dimethylaminopyridine, 10kg of ethanol, 15kg of acetone, 5kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 20kg of hyperbranched polysilane grafted hexagonal boron nitride nano-sheets and 1kg of antioxidant 1010 are added and uniformly mixed, and then ceramic toughening epoxy resin for the halogen-free copper-clad plate can be obtained.
Example 2:
step 1: adding 0.72g of tris (hydroxymethyl) aminomethane into 500g of deionized water, regulating the pH to 8.1 by using dilute hydrochloric acid, adding 1.6g of dopamine hydrochloride after uniformly mixing, continuously stirring for 18min, adding 3.2g of hexagonal boron nitride nano-sheets, performing ultrasonic dispersion for 2h, heating to 55 ℃ in a water bath, and standing for reaction for 22h to obtain polydopamine-loaded hexagonal boron nitride nano-sheets;
step 2: adding 0.53g of polydopamine-loaded hexagonal boron nitride nano-sheet into 8.2g of tetrahydrofuran, adding 1.1g of glacial acetic acid, heating to 70 ℃ in a water bath, adding 2.1g of gamma-glycidol ether oxypropyl trimethoxysilane, refluxing for 25h, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nano-sheet;
step 3: 91kg of bisphenol A epoxy resin is heated to 55 ℃, 22kg of maleic anhydride, 0.33kg of 4-dimethylaminopyridine, 12kg of ethanol, 16kg of acetone, 5.4kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 21kg of hyperbranched polysilane grafted hexagonal boron nitride nano-sheets and 1.15kg of antioxidant 1010 are added and uniformly mixed, and the ceramic toughening epoxy resin for the halogen-free copper-clad plate can be obtained.
Example 3:
step 1: adding 0.75g of tris (hydroxymethyl) aminomethane into 525g of deionized water, regulating the pH to 8.15 by using dilute hydrochloric acid, adding 1.56g of dopamine hydrochloride after uniformly mixing, continuously stirring for 20min, adding 3.5g of hexagonal boron nitride nano-sheets, performing ultrasonic dispersion for 2-3 h, heating to 55-65 ℃ in a water bath, and standing for reaction for 20-30 h to obtain polydopamine-loaded hexagonal boron nitride nano-sheets;
step 2: adding 0.55g of polydopamine-loaded hexagonal boron nitride nano-sheet into 8.6g of tetrahydrofuran, adding 1.3g of glacial acetic acid, heating to 75 ℃ in a water bath, adding 2.4g of gamma-glycidol ether oxypropyl trimethoxysilane, refluxing for 26 hours, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nano-sheet;
step 3: 93kg of bisphenol A epoxy resin is heated to 55 ℃, 22.5kg of maleic anhydride, 0.38kg of 4-dimethylaminopyridine, 14kg of ethanol, 15.8kg of acetone, 8kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 24.3kg of hyperbranched polysilane grafted hexagonal boron nitride nano-sheets and 1.5kg of antioxidant 1010 are added and uniformly mixed, and then the ceramic toughening epoxy resin for the halogen-free copper clad laminate can be obtained.
Example 4:
step 1: adding 0.8g of tris (hydroxymethyl) aminomethane into 550g of deionized water, regulating the pH to 8.3 by using dilute hydrochloric acid, adding 1.7g of dopamine hydrochloride after uniformly mixing, continuously stirring for 21min, adding 3.4g of hexagonal boron nitride nano-sheets, performing ultrasonic dispersion for 2.5h, heating to 60 ℃ in a water bath, and standing for reaction for 24h to obtain polydopamine-loaded hexagonal boron nitride nano-sheets;
step 2: adding 0.64g of polydopamine-loaded hexagonal boron nitride nano-sheet into 8.9g of tetrahydrofuran, adding 1.7g of glacial acetic acid, heating to 75 ℃ in a water bath, adding 2.35g of gamma-glycidol ether oxypropyl trimethoxysilane, refluxing for 26 hours, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nano-sheet;
step 3: 100kg of bisphenol A epoxy resin is heated to 55 ℃, 26kg of maleic anhydride, 0.42kg of 4-dimethylaminopyridine, 13kg of ethanol, 16.5kg of acetone, 10kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 26kg of hyperbranched polysilane grafted hexagonal boron nitride nano-sheets and 1.7kg of antioxidant 1010 are added and uniformly mixed, and the ceramic toughening epoxy resin for the halogen-free copper-clad plate can be obtained.
Example 5:
step 1: adding 0.85g of tris (hydroxymethyl) aminomethane into 580g of deionized water, regulating the pH to 8.3 by using dilute hydrochloric acid, adding 1.8g of dopamine hydrochloride after uniformly mixing, continuously stirring for 18min, adding 3.75g of hexagonal boron nitride nano-sheets, performing ultrasonic dispersion for 2.5h, heating to 60 ℃ in a water bath, and standing for reaction for 27h to obtain polydopamine-loaded hexagonal boron nitride nano-sheets;
step 2: adding 0.68g of polydopamine-loaded hexagonal boron nitride nano-sheet into 9.2g of tetrahydrofuran, adding 1.6g of glacial acetic acid, heating to 75 ℃ in a water bath, adding 2.6g of gamma-glycidol ether oxypropyl trimethoxysilane, refluxing for 27h, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nano-sheet;
step 3: 110kg of bisphenol A epoxy resin is heated to 55 ℃, 26kg of maleic anhydride, 0.54kg of 4-dimethylaminopyridine, 17kg of ethanol, 16.5kg of acetone, 12kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 28kg of hyperbranched polysilane grafted hexagonal boron nitride nano-sheets and 1.85kg of antioxidant 1010 are added and uniformly mixed, and the ceramic toughening epoxy resin for the halogen-free copper-clad plate can be obtained.
Example 6:
step 1: adding 0.86g of tris (hydroxymethyl) aminomethane into 575g of deionized water, regulating the pH to 8.25 by using dilute hydrochloric acid, adding 1.76g of dopamine hydrochloride after uniformly mixing, continuously stirring for 25min, adding 3.6g of hexagonal boron nitride nano-sheets, performing ultrasonic dispersion for 2.6h, heating to 60 ℃ in a water bath, and standing for reaction for 23h to obtain polydopamine-loaded hexagonal boron nitride nano-sheets;
step 2: adding 0.69g of polydopamine-loaded hexagonal boron nitride nano-sheet into 9.3g of tetrahydrofuran, adding 1.5g of glacial acetic acid, heating to 75 ℃ in a water bath, adding 2.65g of gamma-glycidol ether oxypropyl trimethoxysilane, refluxing for 28h, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nano-sheet;
step 3: 110kg of bisphenol A epoxy resin is heated to 55 ℃, 28kg of maleic anhydride, 0.53kg of 4-dimethylaminopyridine, 17.3kg of ethanol, 17.5kg of acetone, 13.6kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 24.9kg of hyperbranched polysilane grafted hexagonal boron nitride nano-sheets and 1.77kg of antioxidant 1010 are added and uniformly mixed, and the ceramic toughening epoxy resin for the halogen-free copper clad laminate can be obtained.
Example 7:
step 1: adding 0.85g of tris (hydroxymethyl) aminomethane into 590g of deionized water, regulating the pH to 8.3 by using dilute hydrochloric acid, adding 1.95g of dopamine hydrochloride after uniformly mixing, continuously stirring for 28min, adding 3.8g of hexagonal boron nitride nano-sheets, performing ultrasonic dispersion for 2.5h, heating to 60 ℃ in a water bath, and standing for reaction for 25h to obtain polydopamine-loaded hexagonal boron nitride nano-sheets;
step 2: adding 0.78g of polydopamine-loaded hexagonal boron nitride nano-sheet into 9.6g of tetrahydrofuran, adding 1.95g of glacial acetic acid, heating to 75 ℃ in a water bath, adding 2.86g of gamma-glycidol ether oxypropyl trimethoxysilane, refluxing for 29 hours, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nano-sheet;
step 3: 115kg of bisphenol A epoxy resin is heated to 55 ℃, 29kg of maleic anhydride, 0.58kg of 4-dimethylaminopyridine, 19kg of ethanol, 18kg of acetone, 14.8kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 28.5kg of hyperbranched polysilane grafted hexagonal boron nitride nano-sheets and 1.3kg of antioxidant 1010 are added and uniformly mixed, and the ceramic toughening epoxy resin for the halogen-free copper-clad plate can be obtained.
Example 8:
step 1: adding 1g of tris (hydroxymethyl) aminomethane into 600g of deionized water, regulating the pH to 8.5 by using dilute hydrochloric acid, uniformly mixing, adding 2g of dopamine hydrochloride, continuously stirring for 30min, adding 4g of hexagonal boron nitride nanosheets, performing ultrasonic dispersion for 3h, heating to 65 ℃ in a water bath, and standing for 30h to obtain polydopamine-loaded hexagonal boron nitride nanosheets;
step 2: adding 0.8g of polydopamine-loaded hexagonal boron nitride nanosheets into 10g of tetrahydrofuran, adding 2g of glacial acetic acid, heating to 80 ℃ in a water bath, adding 3g of gamma-glycidol ether oxypropyl trimethoxysilane, refluxing for 30h, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nanosheets;
step 3: 120kg of bisphenol A epoxy resin is heated to 60 ℃, 30kg of maleic anhydride, 0.6kg of 4-dimethylaminopyridine, 20kg of ethanol, 20kg of acetone, 15kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 30kg of hyperbranched polysilane grafted hexagonal boron nitride nano-sheets and 2kg of antioxidant 1010 are added and uniformly mixed, and then ceramic toughening epoxy resin for the halogen-free copper-clad plate can be obtained.
Comparative example 1:
epoxy hyperbranched polysilane grafted hexagonal boron nitride nano-sheets are not added.
90kg of bisphenol A epoxy resin is heated to 50 ℃, 20kg of maleic anhydride, 0.3kg of 4-dimethylaminopyridine, 10kg of ethanol, 15kg of acetone, 5kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1kg of antioxidant 1010 are added and uniformly mixed, and then ceramic toughening epoxy resin for the halogen-free copper-clad plate can be obtained.
Comparative example 2:
directly adding hexagonal boron nitride nano-sheet.
91kg of bisphenol A epoxy resin is heated to 55 ℃, 22kg of maleic anhydride, 0.33kg of 4-dimethylaminopyridine, 12kg of ethanol, 16kg of acetone, 5.4kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 21kg of hexagonal boron nitride nano-sheets and 1.15kg of antioxidant 1010 are added and uniformly mixed, and then ceramic toughening epoxy resin for the halogen-free copper-clad plate can be obtained.
Comparative example 3:
directly adding the polydopamine-loaded hexagonal boron nitride nano-sheet.
Step 1: adding 0.75g of tris (hydroxymethyl) aminomethane into 525g of deionized water, regulating the pH to 8.15 by using dilute hydrochloric acid, adding 1.56g of dopamine hydrochloride after uniformly mixing, continuously stirring for 20min, adding 3.5g of hexagonal boron nitride nano-sheets, performing ultrasonic dispersion for 2-3 h, heating to 55-65 ℃ in a water bath, and standing for reaction for 20-30 h to obtain polydopamine-loaded hexagonal boron nitride nano-sheets;
step 2: 93kg of bisphenol A epoxy resin is heated to 55 ℃, 22.5kg of maleic anhydride, 0.38kg of 4-dimethylaminopyridine, 14kg of ethanol, 15.8kg of acetone, 8kg of 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 24.3kg of hexagonal boron nitride nano-sheet loaded with polydopamine and 1.5kg of antioxidant 1010 are added and uniformly mixed, and the ceramic toughening epoxy resin for the halogen-free copper clad laminate can be obtained.
Experiment:
examples 1 to 8 and comparative examples 1 to 3 were tested and the experimental results are shown in the following table. Wherein:
and (3) testing heat conduction performance: the thermal diffusivity (α) was measured using a laser flash instrument (FLA-467), the sample diameter was 100mm, the sample thickness was 2mm, and the sample thermal conductivity was calculated by the formula λ=α×c p ×ρ；
Tensile strength test: cutting a sample into a size of 4mm multiplied by 75mm multiplied by 2mm according to GB/T1040-92, and placing the sample in an electronic universal testing machine (product number AG-201, shimadzu Japan) for a tensile test, wherein the tensile speed is 100mm/min;
thermal stability: heating to 500 ℃ under nitrogen at a heating rate of 5 ℃/min, and recording the temperature T of 10% of heat loss 10％ 。
Conclusion:
the data of examples 1-8 show that the epoxy resin prepared by the invention has excellent performance and can be used for preparing copper-clad plates. With the example 1 as a reference, the data of the comparative example 1 show that the heat conduction performance, the mechanical performance and the heat resistance of the hyperbranched polysilane grafted hexagonal boron nitride nanosheets on the epoxy resin are all improved. With the example 2 as a reference, the data of the comparative example 2 show that the performance of the material is not improved obviously by directly using the hexagonal boron nitride nano-sheets for the modification of the epoxy resin, mainly because the boron nitride nano-sheets have stable chemical properties, lack active groups on the surfaces, and poor dispersibility due to lack of interaction after being blended with the epoxy resin, so that the modification effect is poor; with example 3 as a reference, the data of comparative example 3 shows that although the heat conduction performance, the mechanical performance and the heat resistance of the epoxy resin are obviously improved after the polydopamine-loaded hexagonal boron nitride nanosheets are blended with the epoxy resin, the modification effect is not as good as that of example 3, which shows that after the polydopamine is coated, the compatibility between the hexagonal boron nitride and the epoxy resin is improved; meanwhile, in the embodiment 3, hyperbranched reaction is carried out on the polydopamine-loaded hexagonal boron nitride nanosheets, so that the epoxy hyperbranched polysilane grafted hexagonal boron nitride nanosheets with the three-dimensional network structure are better in compatibility with epoxy resin, and therefore the heat conducting property, the mechanical property and the heat resisting property are further improved.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. 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 (9)
1. The preparation method of the ceramic toughening epoxy resin for the halogen-free copper-clad plate is characterized by comprising the following steps of:
step 1: adding tris (hydroxymethyl) aminomethane into deionized water, regulating the pH to 8-8.5 by using dilute hydrochloric acid, uniformly mixing, adding dopamine hydrochloride, continuously stirring for 15-30 min, adding hexagonal boron nitride nanosheets, uniformly dispersing by ultrasonic waves, heating in a water bath, and standing for reaction to obtain polydopamine-loaded hexagonal boron nitride nanosheets; wherein the dosages of the components are, by weight, 0.7-1 part of tris (hydroxymethyl) aminomethane, 500-600 parts of deionized water, 1.5-2 parts of dopamine hydrochloride and 3-4 parts of hexagonal boron nitride nano-sheets;
step 2: adding polydopamine-loaded hexagonal boron nitride nanosheets into tetrahydrofuran, adding glacial acetic acid, heating in a water bath, heating, adding gamma-glycidol ether oxypropyl trimethoxy silane, refluxing, washing and drying to obtain epoxy hyperbranched polysilane grafted hexagonal boron nitride nanosheets;
step 3: and heating bisphenol A epoxy resin, adding a curing agent, a curing accelerator, ethanol, acetone, a flame retardant, hyperbranched polysilane grafted hexagonal boron nitride nanosheets and an antioxidant, and uniformly mixing to obtain the ceramic toughening epoxy resin for the halogen-free copper-clad plate.
2. The preparation method of the ceramic toughening epoxy resin for the halogen-free copper-clad plate, which is disclosed in claim 1, is characterized by comprising the following steps: in the step 1, the ultrasonic dispersion time is 2-3 hours; the heating temperature of the water bath is 55-65 ℃; and the standing reaction time is 20-30 h.
3. The preparation method of the ceramic toughening epoxy resin for the halogen-free copper-clad plate, which is disclosed in claim 1, is characterized by comprising the following steps: in the step 2, the dosages of the components are, by weight, 0.5-0.8 part of polydopamine-loaded hexagonal boron nitride nano-sheet, 8-10 parts of tetrahydrofuran, 1-2 parts of glacial acetic acid and 2-3 parts of gamma-glycidol ether oxypropyl trimethoxysilane.
4. The preparation method of the ceramic toughening epoxy resin for the halogen-free copper-clad plate, which is disclosed in claim 1, is characterized by comprising the following steps: in the step 2, the water bath heating temperature is 70-80 ℃; the reflow time is 20-24 hours.
5. The preparation method of the ceramic toughening epoxy resin for the halogen-free copper-clad plate, which is disclosed in claim 1, is characterized by comprising the following steps: in the step 3, in the ceramic toughening epoxy resin for the halogen-free copper-clad plate, the content of each component is 90-120 parts by weight of bisphenol A epoxy resin, 20-30 parts by weight of curing agent, 0.3-0.6 part by weight of curing accelerator, 10-20 parts by weight of ethanol, 15-20 parts by weight of acetone, 5-15 parts by weight of flame retardant, 20-30 parts by weight of hyperbranched polysilane grafted hexagonal boron nitride nanosheets and 1-2 parts by weight of antioxidant.
6. The preparation method of the ceramic toughening epoxy resin for the halogen-free copper-clad plate, which is disclosed in claim 1, is characterized by comprising the following steps: in the step 3, the curing agent is any one of diethylenetriamine, maleic anhydride, tetraethylenepentamine, phthalic anhydride and m-phenylenediamine; the curing accelerator is any one of 4-dimethylaminopyridine, 2-methylimidazole and 2-phenylimidazole.
7. The preparation method of the ceramic toughening epoxy resin for the halogen-free copper-clad plate, which is disclosed in claim 1, is characterized by comprising the following steps: in the step 3, the antioxidant is any one of an antioxidant 1010, an antioxidant 1076, an antioxidant 168, an antioxidant 1098 and an antioxidant 264; the flame retardant is any one of tri (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, zinc borate, aluminum hydroxide, magnesium hydroxide and ammonium polyphosphate.
8. The preparation method of the ceramic toughening epoxy resin for the halogen-free copper-clad plate, which is disclosed in claim 1, is characterized by comprising the following steps: in the step 3, the heating temperature of the bisphenol A epoxy resin is 50-60 ℃.
9. The ceramic toughened epoxy resin for halogen-free copper-clad plates, which is prepared by the preparation method of the ceramic toughened epoxy resin for halogen-free copper-clad plates, according to any one of claims 1-8.
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| CN116426086A (en) * | 2023-06-07 | 2023-07-14 | 华北电力大学 | Preparation method of epoxy resin/boron nitride composite material with high surface charge dissipation rate |
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