CN107759977A - Modified epoxy resin-based prepreg for copper-clad plate and preparation method thereof - Google Patents
Modified epoxy resin-based prepreg for copper-clad plate and preparation method thereof Download PDFInfo
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- CN107759977A CN107759977A CN201710851756.0A CN201710851756A CN107759977A CN 107759977 A CN107759977 A CN 107759977A CN 201710851756 A CN201710851756 A CN 201710851756A CN 107759977 A CN107759977 A CN 107759977A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 title abstract description 5
- 229920000647 polyepoxide Polymers 0.000 title abstract description 5
- 239000004593 Epoxy Substances 0.000 claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000006260 foam Substances 0.000 claims abstract description 31
- 239000003292 glue Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000012779 reinforcing material Substances 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 22
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- JBVSBLLOZVDAAZ-UHFFFAOYSA-N 2-diazonio-1-[(2-methylpropan-2-yl)oxy]ethenolate Chemical compound CC(C)(C)OC([O-])=C[N+]#N JBVSBLLOZVDAAZ-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 12
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 claims description 11
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 11
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 11
- 229940057402 undecyl alcohol Drugs 0.000 claims description 11
- 229940071125 manganese acetate Drugs 0.000 claims description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 10
- RDNPPYMJRALIIH-UHFFFAOYSA-N 3-methylcyclohex-3-ene-1,1,2,2-tetracarboxylic acid Chemical compound CC1=CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O RDNPPYMJRALIIH-UHFFFAOYSA-N 0.000 claims description 9
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 claims description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 9
- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- -1 nitrite tert-butyl Chemical compound 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 5
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 claims description 5
- 150000001718 carbodiimides Chemical class 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000003063 flame retardant Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000008054 signal transmission Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000004643 cyanate ester Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- AZAKMLHUDVIDFN-UHFFFAOYSA-N tert-butyl nitrate Chemical compound CC(C)(C)O[N+]([O-])=O AZAKMLHUDVIDFN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WZZFZXZRKPNZOC-UHFFFAOYSA-N 3-nitrobenzenesulfonic acid;pyridine Chemical compound C1=CC=[NH+]C=C1.[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 WZZFZXZRKPNZOC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKRHDMPWBFBQDZ-UHFFFAOYSA-N n'-hexylmethanediimine Chemical compound CCCCCCN=C=N JKRHDMPWBFBQDZ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 229940042129 topical gel Drugs 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a modified epoxy resin-based prepreg for a copper-clad plate and a preparation method thereof, and the preparation method comprises the following steps of adding a modified silicon dioxide foam system into a bifunctional epoxy system, stirring for 30 minutes at 120 ℃, then adding a monofunctional epoxy system and nano hollow alumina at 95-105 ℃, and stirring for 20 minutes to obtain a glue solution; adjusting the solid content of the glue solution to 55-60% by using PMA, and then soaking the reinforcing material in the glue solution to obtain a prepreg; the prepreg is heated and dried to obtain the modified epoxy resin-based prepreg for the copper-clad plate, and then the modified epoxy resin-based copper-clad plate is prepared.
Description
Technical field
The invention belongs to electronics technical field of composite materials, and in particular to a kind of copper-clad plate is solid with modified epoxy base half
Change piece and preparation method thereof, obtained product can be used for Aero-Space, signal transmission, telecommunications field.
Background technology
With the continuous development of scientific technology, the application of polymer-based composite is more and more extensive.Meanwhile each application
Field also proposes higher requirement to different materials accordingly.The most advanced branches of science skill particularly as aerospace industry
Art field, it is more harsh to the performance requirement of material, such as they require composite will have high specific strength, high specific stiffness,
The performances such as high temperature resistant, resistance to ablation.Copper-clad plate is obtained by glass cloth and the resin bed being attached on the glass cloth with conductor layer hot pressing
Arrive, therefore the main performance of pcb board, particularly signal transmission performance are determined by CCL, while CCL performance is closed with resin matrix
System is very big.The relative dielectric coefficient of material is smaller, and the transmission speed of signal is faster；Dielectric loss factor is smaller, and signal is transmitting
During loss power keep one timing, it is allowed to the frequency of transmission is higher, i.e., in the case where signal frequency is identical, dielectric loss value
Smaller, distortion rate is lower in signals transmission.
With fire-retardant attention, it is desirable to which product has fire resistance, fire-retardant to have class requirement, respectively UL94 V-
2nd, UL94 V-1 and UL94 V-0 ranks, wherein UL94 V-0 ranks are the whether fire-retardant international standard of existing judgement material.
Equalization point is found between fire prevention and environmental protection, is the important node of following flame retardant products development.Fire retardant is in modern society
Importance be can not be ignored, but as a series of environmental protection policies in Europe are put into effect, its development and application is restricted to some extent.Such as
While where support personnel and property are from fire threat, and can makes fire retardant drop potential hazard existing for human body and environment
To minimum, be domestic fire retardant manufacturing enterprise, research institution and downstream electronic electrically, building materials, the industry such as traffic and furniture it is common
Focus of attention.The introducing of phosphorus-containing compound in the resin matrix of copper-clad plate is prepared, turns into the main skill of copper-clad plate halogen-free flameproof
Art route.At present, reactive phosphorus flame retardant widely used on copper-clad plate field is mainly DOPO class compounds, with phosphorous ring
Based on oxygen tree fat, phosphorus containing phenolic resin, phosphorus content is between 2-10%, however, being found in practical application, DOPO classes compound tool
There are larger water absorption rate and higher dielectric constant, and the humidity resistance of its manufactured sheet material is low.Simple resin can not
Meet the application of copper-clad plate, even if the preferable cyanate ester resin of heat resistance, it has excellent dielectric properties（Dielectric coefficient：
2.8~3.2；Dielectric loss factor：0.002~0.003）, high-fire resistance（Glass transition temperature：280~295 DEG C）, simultaneously
Cyanate ester resin also has a low-shrinkage, excellent mechanical property and adhesive property etc., and also because solidification deficiency, fragility are big etc. lacks
Fall into and fail to widely apply in copper-clad plate field.So using complex technique, the advantages of being not only to integrate organic-inorganic material, go back
The organic component that compatibility is different is wanted, is hopeful to prepare the copper-clad plate for meeting commercial Application.
The content of the invention
It is an object of the invention to provide a kind of copper-clad plate modified epoxy base prepreg, the modification ring thus prepared
Epoxy resin-based copper-clad plate has excellent dielectric properties, excellent heat resistance, anti-flammability, can be used as electronic signal transmission material should
With.
To achieve the above object of the invention, the technical solution adopted by the present invention is：
A kind of copper-clad plate preparation method of modified epoxy base prepreg, comprises the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added
Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed
Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At room temperature, 3 are mixed, 3 '-dithiodipropionic acid, dichloromethane, acetone；Then m-nitrobenzene sulfonic acid pyridiniujm is added
With manganese acetate, stirring adds methyl butynol after 30 minutes, stirring adds 2,3- epoxy radicals cyclopenta ring amyl groups after 3 hours
Ether, stirring add methylcyclohexene tetracarboxylic dianhydride after 50 minutes, continue stirring 20 minutes；Then N, N-dicyclohexyl are added
Carbodiimide, continue stirring 10 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO
In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy
System；
（4）Improved silica foam system is added in difunctional epoxy systems, 120 DEG C are stirred 30 minutes, then in 95
At~105 DEG C, simple function group epoxy systems, nano-hollow aluminum oxide are added, stirs 20 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then reinforcing material is immersed in glue, obtains prepreg；In advance
After heated drying is expected in leaching, copper-clad plate modified epoxy base prepreg is obtained.
A kind of copper-clad plate modified epoxy base prepreg, its preparation method comprise the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added
Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed
Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At room temperature, 3 are mixed, 3 '-dithiodipropionic acid, dichloromethane, acetone；Then m-nitrobenzene sulfonic acid pyridiniujm is added
With manganese acetate, stirring adds methyl butynol after 30 minutes, stirring adds 2,3- epoxy radicals cyclopenta ring amyl groups after 3 hours
Ether, stirring add methylcyclohexene tetracarboxylic dianhydride after 50 minutes, continue stirring 20 minutes；Then N, N-dicyclohexyl are added
Carbodiimide, continue stirring 10 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO
In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy
System；
（4）Improved silica foam system is added in difunctional epoxy systems, 120 DEG C are stirred 30 minutes, then in 95
At~105 DEG C, simple function group epoxy systems, nano-hollow aluminum oxide are added, stirs 20 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then reinforcing material is immersed in glue, obtains prepreg；In advance
After heated drying is expected in leaching, copper-clad plate modified epoxy base prepreg is obtained.
In the present invention, step（1）In, the nanometer titanium dioxide silicon foam, propionate, the diazoacetic acid tert-butyl ester, Asia
The nitric acid tert-butyl ester, tetramethylethylenediamine, the mass ratio of di lauric dibutyl zinc are 1: 3: 1: 1.5: 1.5: 0.005.The present invention
The creative di lauric dibutyl zinc that first passes through is catalyst, and it is organic to form reactivity in the particle surface of silicon dioxide foam
Thing, it is different from existing coupling agent surface treatment, obtained nanometer titanium dioxide silicon foam is reacted per se with stronger reactive group,
The solidification process that resin compounded system is beneficial to participate in resin is directly used in, the table of filler is on the one hand adjusted by several organic molecular species
Surface properties, preventing inorganic particulate, it produces the too fast influence of partial polymerization to resin, it can in addition contain adjust crosslinked polymer net
Network so that cured product crosslinking is reasonable, is unlikely to that fragility is excessive, and the application of especially several compounds improves the heat-resisting of system
With dielectric properties.
In the present invention, step（2）In, 3,3 '-dithiodipropionic acid, dichloromethane, acetone, m-nitrobenzene sulfonic acid pyridine
Salt, manganese acetate, methyl butynol, 2,3- epoxy radicals cyclopenta rings amyl ether, methylcyclohexene tetracarboxylic dianhydride, N, N-two ring
The mass ratio of hexyl carbodiimide is 0.015: 0.05: 0.8: 0.0013: 0.001: 0.01: 1: 0.12: 0.08；Add methyl fourth
The time of alkynol is 20 minutes；Before epoxy is added, two sulphur diine butyl dipropionates are prepared for first, and due to its amount
It is few, high polymer main chain can be accessed with epoxy reaction, fire-retardant while heat-resisting and dielectric properties will not be reduced, can also improved resistance to
It is damp and hot.
In the present invention, step（3）In, graphene oxide, isomery undecyl alcohol APEO, phthalic acid two shrink sweet
The mass ratio of pungent two mercaptan of grease, 1,8- is 0.001: 0.08: 1: 0.15.This is very crucial, graphene from being not used in copper-clad plate,
Because its conductive energy, with copper-clad plate dielectric layer insulating properties on the contrary, still it has good performance, the invention
Selective oxidation graphene, and first mixed with isomery undecyl alcohol APEO, add in epoxy, graphite can be greatly improved
The reactivity and decentralization of alkene so that graphene avoids gathering while playing catalytic performance.
In the present invention, step（4）In, improved silica foam system, difunctional epoxy systems, simple function group epoxy
System, the mass ratio of hollow alumina are 0.3: 0.4: 1: 0.005.The present invention uses simple function group epoxy and difunctional, does not have
There is the four-functional group epoxy using routine, it is still heat-resisting good, processability is also improved, on the one hand due to improved silica foam
Effect, the catalysis of graphene is also critically important in addition, while two sulphur diine butyl dipropionates and pungent two mercaptan of 1,8- can all strengthen
Acid anhydrides/amine solidification effect.
In the present invention, step（5）In, in the prepreg, the mass fraction of reinforcing material is 30~35%；The increasing
Strong material is electronic-grade glass fiber cloth；The heat drying is 140 DEG C/30s+170 DEG C/40s+195 DEG C/20s, and this is for this
Invent critically important, especially ensure stability of the graphene in hot-press solidifying, avoid local conductivity issues, while ladder liter
The effect of the compatilizer of temperature and small molecule, the presence of bubble, pin hole is turn avoid, while provided using very small amount hollow alumina
Certain diluting effect, topical gel transition is avoided, good basis is laid for hot-press solidifying.The present invention passes through overall compatibility and work
Skill designs, obtained epoxy radicals copper-clad plate is heat-resisting very well, dielectric is fine, it is fire-retardant very well, hydroscopicity it is low, other performances all meet
IPC is marked.
The present invention is first with propionate, the diazoacetic acid tert-butyl ester, nitrite tert-butyl, tetramethylethylenediamine monomer to receiving
Rice silicon dioxide foam processing, improves filler in organic matter, particularly high polymer while reducing filler reactivity
Dispersiveness, the active filler after processing do not interfere with polymer curing process when adding resin prepolymer, improve cross-linked network on the contrary
The density of network, increase flexible points, it is important to propionate, the diazoacetic acid tert-butyl ester, nitrite tert-butyl, tetramethylethylenediamine
Dosage it will not be reacted completely, some small molecule monomers can mix with epoxy with improved silica foam system,
Played a role when hot-press solidifying.The modified filler of material of the present invention simultaneously, avoids conventional fillers and dangling bonds pair be present
The adverse effect of dielectric properties, there is good low-k, can be used as high-frequency electronic material.The present invention is without using fire-retardant
Agent, acted on by modified filler and pungent two mercaptan of two sulphur diine butyl dipropionates, 1,8-, imitated in combination with polymer reaction
Fruit, material can form finer and close protective layer in heated and burning, reach excellent hot oxygen screen effect, solid so as to assign
Body adhesives excellent heat resistance and anti-flammability, while mechanical property, adhesive property are good；Overcome the resistance of prior art filler
Mechanical properties decrease, the problem of heat-resisting decline that the bonding that combustion agent is brought declines and reactive flame retardant is brought.
In the present invention, organic-compound system is the primary bond composition of resin matrix composite system, and rigid Nano filling can be
It is dispersed in evenly in resin, improves the intensity and thermal level of its solidfied material；Particularly present invention, avoiding between compound interface
There is hole, the formation of polymer interpenetration network will not be hindered, ensure the intensity of solidfied material.To organic-inorganic dielectric material
Speech, organic matter is the short slab of heat resistance, several small molecules in material of the invention be present and coordinates under curing agent effect, structure is very
It is stable, and there is extra high heat resistance.The inorganic material purity that includes of system of the present invention is high, ultra-fine, good fluidity, particle diameter
Narrowly distributing, particularly the invention carry out propionate, the diazoacetic acid tert-butyl ester, Asia on silicon dioxide foam surface
The nitric acid tert-butyl ester, tetramethylethylenediamine catalytic reaction, inorganic material external connection active reactive group can improve inorganic particulate
Compatibility between polymer, organic group are connected to the very strong inorganic molecule of heat resistance so that polymer of the invention exists
Remain to keep original state constant thus sufficiently stable under the high temperature conditions under the degradation temperature of general polymerization thing；Initial heat point
Temperature is solved more than 380 DEG C, glass transition temperature more than 210 DEG C, this for not using multi-functional epoxy systems from having no
Report.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art:
Preparation method mesocomplex system composition provided by the invention is reasonable, then prepares technique, in obtained copper-clad plate base material
Inorganic nanoparticles have uniform decentralization in system, and preparation process belongs to chemical process, the inorganic matter and resin of formation
Between surface adhesion be much stronger than the surface adhesion of traditional physical mechanical blending.The material system composition that the present invention utilizes
Rationally, compatibility is good between each component, and modified epoxy base copper-clad plate has thus been prepared, and has good mechanics
Property, heat resistance, meet the development and application of modified epoxy base copper-clad plate；Comprehensive polymer, the component of inorganic particulate two it is excellent
Point, improve two components the shortcomings that, so as to improve to obtain the combination property of material；Solidification effect is good, and cross-linked structure is uniform, small molecule
On the one hand compound as the compatilizer of macromolecule organic, can increase the compatibility of system each component, on the other hand avoid
The defects of crosslinking is uneven is formed during hot-press solidifying, ensures that resin system forms stable structure, particularly improves Conventional epoxy
Heat-resisting, the dielectricity of resin, and fire retardant is free of, by reasonable reaction, it successfully avoid existing reactive phosphor-containing flame-proof point
The defects of son is hygroscopic, achieves unexpected effect.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment one
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added
Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed
Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 25%；
（2）At room temperature, 3 are mixed, 3 '-dithiodipropionic acid, dichloromethane, acetone；Then m-nitrobenzene sulfonic acid pyridiniujm is added
With manganese acetate, stirring adds methyl butynol after 30 minutes（Complete within 20 minutes）, 2,3- epoxy basic rings are added after stirring 3 hours
Amyl group cyclopenta ether, stirring add methylcyclohexene tetracarboxylic dianhydride after 50 minutes, continue stirring 20 minutes；Then N, N are added
- dicyclohexylcarbodiimide, continue stirring 10 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO
In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy
System；
（4）Improved silica foam system is added in difunctional epoxy systems, 120 DEG C are stirred 30 minutes, then in 100
At DEG C, simple function group epoxy systems, nano-hollow aluminum oxide are added, stirs 20 minutes, obtains glue；
（5）It is 60% with PMA regulation glue solid contents, then 1080 glass cloth is immersed in above-mentioned glue, obtain prepreg；
Prepreg obtains copper-clad plate modified epoxy base half after 140 DEG C/30s+170 DEG C/40s+195 DEG C/20s heat dryings
Cured sheets, it contains the mass fraction of glass cloth for 35%；
（6）6 prepregs, hot forming, you can obtain modified epoxy base are placed between half ounce of rolled copper foil of two panels
Copper-clad plate；Performance test is shown in Table 1.
Step（1）In, the nanometer titanium dioxide silicon foam, propionate, the diazoacetic acid tert-butyl ester, the tertiary fourth of nitrous acid
Ester, tetramethylethylenediamine, the mass ratio of di lauric dibutyl zinc are 1: 3: 1: 1.5: 1.5: 0.005；Step（2）In, 3,3 '-
Dithiodipropionic acid, dichloromethane, acetone, m-nitrobenzene sulfonic acid pyridiniujm, manganese acetate, methyl butynol, 2,3- epoxy basic rings
Amyl group cyclopenta ether, methylcyclohexene tetracarboxylic dianhydride, N, the mass ratio of N-dicyclohexylcarbodiimide is 0.015: 0.05:
0.8∶0.0013∶0.001∶0.01∶1∶0.12∶0.08；Step（3）In, graphene oxide, isomery undecyl alcohol APEO,
The mass ratio of pungent two mercaptan of o-phthalic acid diglycidyl ester, 1,8- is 0.001: 0.08: 1: 0.15；Step（4）In, it is modified
Silicon dioxide foam system, difunctional epoxy systems, simple function group epoxy systems, the mass ratio of hollow alumina are 0.3:
0.4∶1∶0.005；Condition during hot pressing is 5kg/cm2/190℃/20min+5kg/cm2/200℃/40min+8kg/cm2/220
DEG C/140min+ Temperature falls.
Comparative example one
As embodiment one, wherein step（1）Nanometer titanium dioxide silicon foam is handled only with 1%KH550.
Comparative example two
As embodiment one, wherein step（2）It is added without m-nitrobenzene sulfonic acid pyridiniujm and manganese acetate.
Comparative example three
As embodiment one, wherein step（3）It is added without graphene oxide.
Comparative example four
As embodiment one, wherein step（3）It is added without isomery undecyl alcohol APEO.
Comparative example five
As embodiment one, wherein step（4）It is added without nano-hollow aluminum oxide.
According to mechanical performance of the IPC standard methods to the sheet material in the embodiment and comparative example of above-mentioned preparation, dielectricity
Energy and hot property, adhesive property, water absorption rate are determined, as a result referring to table 1.
The performance of the modified epoxy base copper-clad plate of table 1
To sum up, copper-clad plate disclosed by the invention is formed reasonable with modified epoxy base prepreg, compatible between each component
Property it is good, modified epoxy base copper-clad plate has thus been prepared, there is good fire resistance, excellent heat resistance, it is special
Hydroscopicity that Ju You be not low, and other performances all meet standard；Meet the development and application of modified epoxy base copper-clad plate.
Claims (10)
1. a kind of copper-clad plate preparation method of modified epoxy base prepreg, comprises the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added
Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed
Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At room temperature, 3 are mixed, 3 '-dithiodipropionic acid, dichloromethane, acetone；Then m-nitrobenzene sulfonic acid pyridiniujm is added
With manganese acetate, stirring adds methyl butynol after 30 minutes, stirring adds 2,3- epoxy radicals cyclopenta ring amyl groups after 3 hours
Ether, stirring add methylcyclohexene tetracarboxylic dianhydride after 50 minutes, continue stirring 20 minutes；Then N, N-dicyclohexyl are added
Carbodiimide, continue stirring 10 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO
In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy
System；
（4）Improved silica foam system is added in difunctional epoxy systems, 120 DEG C are stirred 30 minutes, then in 95
At~105 DEG C, simple function group epoxy systems, nano-hollow aluminum oxide are added, stirs 20 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then reinforcing material is immersed in glue, obtains prepreg；In advance
After heated drying is expected in leaching, copper-clad plate modified epoxy base prepreg is obtained.
2. the preparation method of copper-clad plate modified epoxy base prepreg according to claim 1, it is characterised in that：Step
Suddenly（1）In, the nanometer titanium dioxide silicon foam, propionate, the diazoacetic acid tert-butyl ester, nitrite tert-butyl, tetramethyl second
Diamines, the mass ratio of di lauric dibutyl zinc are 1: 3: 1: 1.5: 1.5: 0.005.
3. the preparation method of copper-clad plate modified epoxy base prepreg according to claim 1, it is characterised in that：Step
Suddenly（2）In, 3,3 '-dithiodipropionic acid, dichloromethane, acetone, m-nitrobenzene sulfonic acid pyridiniujm, manganese acetate, methyl butynol,
2,3- epoxy radicals cyclopenta rings amyl ether, methylcyclohexene tetracarboxylic dianhydride, N, the mass ratio of N-dicyclohexylcarbodiimide are
0.015∶0.05∶0.8∶0.0013∶0.001∶0.01∶1∶0.12∶0.08；The time for adding methyl butynol is 20 minutes.
4. the preparation method of copper-clad plate modified epoxy base prepreg according to claim 1, it is characterised in that：Step
Suddenly（3）In, graphene oxide, isomery undecyl alcohol APEO, o-phthalic acid diglycidyl ester, 1,8- pungent two mercaptan
Mass ratio is 0.001: 0.08: 1: 0.15.
5. the preparation method of copper-clad plate modified epoxy base prepreg according to claim 1, it is characterised in that：Step
Suddenly（4）In, improved silica foam system, difunctional epoxy systems, simple function group epoxy systems, the matter of hollow alumina
Amount is than being 0.3: 0.4: 1: 0.005.
6. the preparation method of copper-clad plate modified epoxy base prepreg according to claim 1, it is characterised in that：Step
Suddenly（5）In, in the prepreg, the mass fraction of reinforcing material is 30~35%；The reinforcing material is that E-glass is fine
Wei Bu；The heat drying is 140 DEG C/30s+170 DEG C/40s+195 DEG C/20s.
A kind of 7. copper-clad plate modified epoxy base prepreg, it is characterised in that：The copper-clad plate modified epoxy
The preparation method of base prepreg comprises the following steps：
（1）By nano silicon foam dispersion in toluene, propionate, the diazoacetic acid tert-butyl ester and nitrous are then added
Tert-butyl acrylate；Stirred 15 minutes at 80 DEG C；Then tetramethylethylenediamine is added, the fourth of tin dilaurate two is added after being uniformly dispersed
Base zinc, back flow reaction 7 hours, it is eventually adding acetone and obtains the improved silica foam system that solid content is 20~25%；
（2）At room temperature, 3 are mixed, 3 '-dithiodipropionic acid, dichloromethane, acetone；Then m-nitrobenzene sulfonic acid pyridiniujm is added
With manganese acetate, stirring adds methyl butynol after 30 minutes, stirring adds 2,3- epoxy radicals cyclopenta ring amyl groups after 3 hours
Ether, stirring add methylcyclohexene tetracarboxylic dianhydride after 50 minutes, continue stirring 20 minutes；Then N, N-dicyclohexyl are added
Carbodiimide, continue stirring 10 minutes, obtain simple function group epoxy systems；
（3）Phthalic acid 2-glycidyl is added after graphene oxide is mixed 30 minutes with isomery undecyl alcohol APEO
In ester, 125 DEG C are stirred 20 minutes, then add pungent two mercaptan of 1,8-, are stirred 50 minutes in 130 DEG C, are obtained difunctional epoxy
System；
（4）Improved silica foam system is added in difunctional epoxy systems, 120 DEG C are stirred 30 minutes, then in 95
At~105 DEG C, simple function group epoxy systems, nano-hollow aluminum oxide are added, stirs 20 minutes, obtains glue；
（5）It is 55~60% with PMA regulation glue solid contents, then reinforcing material is immersed in glue, obtains prepreg；In advance
After heated drying is expected in leaching, copper-clad plate modified epoxy base prepreg is obtained.
8. copper-clad plate modified epoxy base prepreg according to claim 7, it is characterised in that：Step（1）In, institute
State nanometer titanium dioxide silicon foam, propionate, the diazoacetic acid tert-butyl ester, nitrite tert-butyl, tetramethylethylenediamine, two bays
The mass ratio of sour dibutyl zinc is 1: 3: 1: 1.5: 1.5: 0.005；Step（2）In, 3,3 '-dithiodipropionic acid, dichloromethane,
Acetone, m-nitrobenzene sulfonic acid pyridiniujm, manganese acetate, methyl butynol, 2,3- epoxy radicals cyclopenta rings amyl ether, methylcyclohexene
Tetracarboxylic dianhydride, N, the mass ratio of N-dicyclohexylcarbodiimide is 0.015: 0.05: 0.8: 0.0013: 0.001: 0.01: 1:
0.12∶0.08；The time for adding methyl butynol is 20 minutes.
9. copper-clad plate modified epoxy base prepreg according to claim 7, it is characterised in that：Step（3）In, oxygen
Graphite alkene, isomery undecyl alcohol APEO, o-phthalic acid diglycidyl ester, the mass ratio of pungent two mercaptan of 1,8- are
0.001∶0.08∶1∶0.15；Step（4）In, improved silica foam system, difunctional epoxy systems, simple function group ring
Oxygen system, the mass ratio of hollow alumina are 0.3: 0.4: 1: 0.005.
10. copper-clad plate modified epoxy base prepreg according to claim 7, it is characterised in that：Step（5）In,
In the prepreg, the mass fraction of reinforcing material is 30~35%；The reinforcing material is electronic-grade glass fiber cloth；Institute
It is 140 DEG C/30s+170 DEG C/40s+195 DEG C/20s to state heat drying.
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