CN115181419A - Method for modifying cyanate ester by vinyl mesoporous silica and polyimide - Google Patents
Method for modifying cyanate ester by vinyl mesoporous silica and polyimide Download PDFInfo
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- CN115181419A CN115181419A CN202210823797.XA CN202210823797A CN115181419A CN 115181419 A CN115181419 A CN 115181419A CN 202210823797 A CN202210823797 A CN 202210823797A CN 115181419 A CN115181419 A CN 115181419A
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- polyimide
- vinyl
- cyanate ester
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- ester resin
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- 239000004643 cyanate ester Substances 0.000 title claims abstract description 123
- 229920001721 polyimide Polymers 0.000 title claims abstract description 84
- 239000004642 Polyimide Substances 0.000 title claims abstract description 82
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 81
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 101
- 229920005989 resin Polymers 0.000 claims abstract description 101
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 39
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002086 nanomaterial Substances 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002114 nanocomposite Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 11
- 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 10
- 238000003756 stirring Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- -1 3, 4-biphenyl tetracarboxylic anhydride Chemical class 0.000 claims description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- OHVGNSMTLSKTGN-BTVCFUMJSA-N [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O Chemical compound [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O OHVGNSMTLSKTGN-BTVCFUMJSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 13
- 239000000805 composite resin Substances 0.000 abstract description 12
- 239000000945 filler Substances 0.000 abstract description 7
- 238000004891 communication Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000011157 advanced composite material Substances 0.000 abstract 1
- 150000002466 imines Chemical class 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 241000143432 Daldinia concentrica Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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Abstract
The invention discloses a method for modifying cyanate by vinyl mesoporous silica and polyimide, which comprises the steps of adding 5-10 parts by weight of polyimide into 100 parts by weight of cyanate at the temperature of 100 ℃, and then adding 1-10 parts by weight of vinyl mesoporous SiO 2 The vinyl mesoporous SiO is obtained after the prepolymerization and the solidification of the nano material 2 A polyimide-cyanate resin composite material. The polyimide and cyanate ester blended resin is used as prepolymer, and the polyimideBenzene rings and nonpolar bonds in imine molecules can increase the free volume of the blended resin so as to reduce the dielectric constant, and can also reduce the curing temperature and curing time of cyanate ester, IPN formed by the cyanate ester can also play a certain toughening role, carbon spheres prepared by glucose hydrothermal reaction are taken as templates, tetraethoxysilane is taken as a silicon source material, and vinyl mesoporous SiO is modified by vinyl trimethoxy silane 2 The nano filler is a nano filler, has good dispersibility and can catalyze cyanate to solidify, and the existence of the nano filler enables the nano filler to obtain good interfacial adhesion in a composite system to improve the toughness of the composite material, and in addition, the introduction of a porous structure can further reduce the dielectric constant, so that the high-performance composite material is prepared, and the nano filler is suitable for preparing advanced composite materials, adhesives and the like in the fields of aerospace, electronic circuits, communication and the like.
Description
Technical Field
The invention relates to the technical field of insulating materials, in particular to a method for modifying cyanate ester by vinyl mesoporous silica and polyimide.
Background
Ultra large scale integrated circuits (ULSI) are rapidly developing in today's society, the integration level of devices is gradually increasing, and the size requirements of semiconductor chips are getting smaller and smaller. As feature sizes are reduced to submicron dimensions, RC delay, crosstalk, power consumption due to parasitic capacitance between Printed Circuit Board (PCB) lines and layers have become a major factor limiting device performance. To solve this problem, much research has been focused on the dielectric properties of materials, and the lower the dielectric constant, the faster the signal transmission speed, and the lower the dielectric loss, the lower the distortion rate during the signal transmission process. Therefore, it is required to develop dielectric constant (D) k ) Materials below 3.0.
Cyanate Ester (CE) resin has a low dielectric constant (epsilon) and dielectric loss (tan delta) value, an extremely low water absorption, good flame retardancy, and excellent heat resistance. In addition, the cyanate ester monomer has low melting point, low viscosity and good process performance. Therefore, CE resins are widely used in the fields of high-performance printed circuit boards, communication satellites, and the like. Nevertheless, the high cyanate curing temperature, the highly crosslinked network and the symmetrical triazine ring structure after cyanate group curing reaction lead to poor toughness of CE resin, which severely limits its wider application.
The commonly used methods for reducing the dielectric constant of materials mainly include two methods: (1) And (3) chemical modification, namely doping a strong electronegativity element into a molecular structure, so that electrons are firmly bound, and the polarity of the material is reduced. The conventional chemical modification method is to dope fluorine into the material to reduce the dielectric constant, but this method has the problems of complicated operation, high cost and insignificant reduction effect. (2) The physical modification is to reduce the density of the material and further reduce the dielectric constant by adding inorganic filler with a porous or hollow structure, or to reduce the dielectric constant of the material by doping low-dielectric polymer into resin, but the physical blending mode has the problem of uneven dispersion, thereby affecting the processing performance and the mechanical property of the material.
The toughness of a resin matrix can be well improved by adopting an interpenetrating network polymer (IPN) which is an elastomer formed by mutually crosslinking polymer monomers through polymerization reaction, WZhanWen and the like (Journal of Polymer research,2020,27 (6): 160) blend thermoplastic polyimides and cyanate ester in different proportions to obtain a PI/CE composite material with a compact network structure, the mechanical property and the thermal stability of the PI/CE composite material are greatly improved, but the dielectric constant of the PI/CE composite material is still higher and cannot meet the requirement of the current low-dielectric material.
In addition to the above mesoporous SiO 2 The introduction of the toughening agent not only can achieve the toughening effect, but also can effectively reduce the dielectric constant of the toughening agent. ZHenZHen et al (Chemistry Letters,2017,46 (1): 139-142) by introducing nanoporous SiO 2 The cyanate ester with lower dielectric constant and enhanced toughness is prepared, more gaps are reserved in the composite material, the dielectric constant is reduced from 3.20 to 3.02, a balance effect is shown in the aspect of improving mechanical and thermal properties, and the impact strength, the bending strength and the bending modulus are slightly increased. Modifying the surface of silica, crosslinking silica with resin matrix, and modifying silica with different functional groups by Z Xuon (Surfaces and Interfaces,2021 (22): 100807) as filler to prepare SiO 2 The research shows that the vinyl modified silicon dioxide can be better combined with the resin matrix phase, and the dielectric constant of the vinyl modified silicon dioxide is 0.15 lower than that of the unmodified silicon dioxide. Thus aiming at CE resin, the CE resin is blended with polyimide to form IPN and vinyl mesoporous SiO is introduced 2 The dielectric property and the toughness of the composite material can be obviously improved.
Disclosure of Invention
Aiming at the problems of poor dielectric property and poor toughness of the existing cyanate ester resin, the invention provides a method for modifying cyanate ester by vinyl mesoporous silica and polyimide. The invention aims to solve the technical problem of providing a method for modifying cyanate by vinyl mesoporous silica and polyimide, which can remarkably improve the toughness of cyanate while maintaining the superior performance of cyanate, and can also effectively reduce the dielectric constant and the curing temperature of cyanate. Mesoporous SiO modified by vinyl trimethoxy silane 2 Can obviously improve the dispersibility in a resin matrix, is not easy to form agglomeration, greatly improves the dielectric property of the cyanate ester resin,in addition, because the polyimide molecules contain a large number of benzene ring structures and nonpolar bonds, a large free volume is provided for the composite material, and the reduction of the dielectric constant of the cyanate ester can also be facilitated. The invention also provides a method for modifying cyanate by vinyl mesoporous silica and polyimide.
The technical scheme adopted by the invention to realize the purpose is as follows: vinyl mesoporous SiO 2 The filled polyimide/cyanate resin is characterized by comprising the following raw material components in percentage by weight: 100 parts of cyanate ester resin, 5-10 parts of polyimide and 1-10 parts of SiO 2 。
The vinyl mesoporous SiO 2 The nano-particles are inorganic nano-particles, and the matrix resin is a copolymer of cyanate ester resin and polyimide resin.
Further, the vinyl mesoporous SiO 2 The nano material is vinyl mesoporous SiO modified by vinyl trimethoxy silane by taking carbon spheres prepared by glucose hydrothermal method as a template and tetraethoxysilane as a silicon source material 2
Furthermore, the cyanate ester resin is one of bisphenol a cyanate ester resin, bisphenol E cyanate ester resin, and bisphenol F cyanate ester resin.
Further, the acid anhydride monomer of the polyimide is one or a mixture of more of pyromellitic dianhydride, dimethylketone tetracarboxylic dianhydride, 3, 4-biphenyl tetracarboxylic anhydride, triphenyl diether tetracarboxylic dianhydride and biphenyl diether dianhydride; the polyamine is one or more of p-phenylenediamine, 4-diphenylsulfone diamine, m-phenylenediamine, 3 '-diaminodiphenyl sulfone, 4' -diaminobenzene, etc.
Furthermore, the catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate and dibutyltin didodecyl sulfenyl.
Furthermore, the cyanate ester resin is 100 parts by mass, and the polyimide is 5-10 parts by mass.
Further, the vinyl mesoporous SiO 2 The mass ratio of the nano material to the cyanate is 0.01-0.1.
The invention also provides a method for modifying cyanate by vinyl mesoporous silica and polyimide, which comprises the following steps:
1. preparing a glucose aqueous solution with a certain concentration in a reaction kettle, carrying out hydrothermal reaction for 12h at 180 ℃, and washing to obtain the glucose carbon spheres.
2. Preparing carbon sphere suspension of carbon spheres, deionized water and ethanol according to a certain proportion, adding a certain amount of CTAB, ammonia water and tetraethoxysilane, stirring for 12h to obtain silicon dioxide suspension, washing and drying for 12h, and calcining for 4h at 550 ℃ in a muffle furnace to obtain mesoporous SiO 2 And (3) powder.
3. Preparing vinyltrimethoxysilane and a deionized water solution according to a certain proportion, reacting for a period of time, and adding the solution into the mesoporous SiO subjected to ultrasonic treatment 2 And in the toluene mixed solution, condensing and refluxing for 18h at the temperature of 80 ℃, washing and drying after the reaction to obtain the vinyl mesoporous SiO 2 。
4. And weighing the cyanate ester resin and the polyimide according to the proportion, heating to melt, and stirring until the mixture is uniform and transparent to obtain the prepolymer resin.
5. Heating the prepolymer grease to 100 ℃, and adding vinyl mesoporous SiO 2 The nano material is magnetically stirred at the temperature to obtain the vinyl mesoporous SiO 2 Polyimide-cyanate ester resin prepolymer.
6. Injecting the nano material into a mold, placing the mold in a vacuum oven, removing air bubbles at 100 ℃, transferring the mold to a forced air drying oven for curing treatment to obtain the vinyl mesoporous SiO 2 A polyimide-cyanate ester resin nano composite material.
The invention has the following beneficial effects: the invention adopts vinyl mesoporous SiO 2 The nano material is used as a filler to prepare the vinyl mesoporous SiO 2 The polyimide-cyanate ester resin nano composite material is characterized in that a certain amount of polyimide is added into cyanate ester resin to form IPN, so that the toughness of the cyanate ester resin can be obviously improved, meanwhile, a large number of benzene ring structures and polar bonds of polyimide molecules can provide a large amount of free volume to reduce the dielectric constant of the polyimide molecules, and the introduced vinyl mesoporous SiO 2 The dielectric property can be obviously improved. In addition, with grapeCarbon spheres prepared by glucose hydrothermal method are used as templates, and mesoporous SiO is obtained by taking CTAB as initiator and calcining at high temperature 2 The morphology structure is relatively regular, and the dispersibility of the modified vinyl trimethoxy silane in a resin matrix is also greatly improved; and compared with pure cyanate ester, the curing temperature and curing time of the material are also greatly reduced. The vinyl mesoporous SiO of the invention 2 The polyimide-cyanate ester resin nano composite material also has excellent thermodynamic property, siO 2 Compared with other porous nanofillers (POSS, MOF) and the like, the nanofiller is simpler to synthesize, and the dielectric property is remarkably improved.
Drawings
FIG. 1 is a vinyl mesoporous SiO 2 TEM image
FIG. 2 is a 5% polyimide/cyanate SEM image
FIG. 3 is a 10% polyimide/cyanate SEM image
FIG. 4 is a 15% polyimide/cyanate SEM image
FIG. 5 is a vinyl mesoporous SiO 2 SEM image of/polyimide-cyanate ester composite material
Detailed Description
The invention is explained in more detail below with reference to the examples and the figures:
example 1
(1) And preparing polyimide: dissolving dianhydride (one or more of pyromellitic dianhydride, dimethylketotetracarboxylic dianhydride, 3, 4-biphenyl tetracarboxylic anhydride, triphendiether tetracarboxylic dianhydride and biphenyl ether dianhydride) and diamine (one or more of p-phenylenediamine, 4-diphenyl sulfone diamine, m-phenylenediamine, 3' -diaminodiphenyl sulfone and 4,4' -diaminobenzene) in N, N-Dimethylformamide (DMF) (in a molar ratio of pyromellitic dianhydride to 4,4' -diaminobenzene of 1).
(2) And preparing a polyimide/cyanate ester resin prepolymer: at 100 ℃, 0.5g of polyimide is added into a beaker filled with 10g of cyanate ester, and after the polyimide is melted, the mixture is stirred for 30min to obtain uniform transparent liquid, thus obtaining the polyimide/cyanate ester resin prepolymer.
(3) And preparing the polyimide/cyanate resin composite material: injecting the polyimide/cyanate ester resin prepolymer obtained in the step (2) into an aluminum mould while the prepolymer is hot, then transferring the prepolymer into a vacuum oven, vacuumizing the vacuum oven for 30min at 100 ℃, transferring the prepolymer into a forced air drying oven for curing after vacuumizing is finished, wherein the curing procedure is as follows: 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h +240 ℃/2h, and finally the polyimide/cyanate composite is obtained.
Comparative example 1
(1) And preparing a cyanate ester resin prepolymer: at 100 ℃, 10g of cyanate ester is added into a beaker, and after the cyanate ester is melted, the mixture is stirred for 30min to obtain uniform transparent liquid, thus obtaining the cyanate ester resin prepolymer.
(2) Preparing cyanate ester resin: injecting the cyanate ester resin prepolymer obtained in the step (1) into an aluminum mould while the cyanate ester resin prepolymer is hot, then transferring the cyanate ester resin prepolymer into a vacuum oven, vacuumizing for 30min at 100 ℃, and transferring the cyanate ester resin prepolymer into an air-blowing drying oven for curing after vacuumizing, wherein the curing procedure is as follows: 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h +240 ℃/2h, and finally the cyanate ester resin is obtained.
Example 2
(1) The polyimide was prepared in the same manner as in example 1.
(2) And preparing a polyimide/cyanate ester resin prepolymer: at 100 ℃, 1.0g of polyimide is added into a beaker filled with 10g of cyanate ester, and after the polyimide is melted, the mixture is stirred for 30min to obtain uniform transparent liquid, thus obtaining the polyimide/cyanate ester resin prepolymer.
(3) And preparing the polyimide/cyanate resin composite material: injecting the polyimide/cyanate ester resin prepolymer obtained in the step (2) into an aluminum mould while the prepolymer is hot, then transferring the prepolymer into a vacuum oven, vacuumizing the vacuum oven for 30min at 100 ℃, transferring the prepolymer into a forced air drying oven for curing after vacuumizing is finished, wherein the curing procedure is as follows: 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h +240 ℃/2h, and finally the polyimide/cyanate composite is obtained.
Example 3
(1) The polyimide was prepared in the same manner as in example 1.
(2) And preparing a polyimide/cyanate ester resin prepolymer: at 100 ℃, 1.5g of polyimide is added into a beaker filled with 10g of cyanate ester, and after the polyimide is melted, the mixture is stirred for 30min to obtain uniform transparent liquid, thus obtaining the polyimide/cyanate ester resin prepolymer.
(3) And preparing the polyimide/cyanate ester resin composite material: injecting the polyimide/cyanate ester resin prepolymer obtained in the step (2) into an aluminum mould while the prepolymer is hot, then transferring the prepolymer into a vacuum oven, vacuumizing the vacuum oven for 30min at 100 ℃, transferring the prepolymer into a forced air drying oven for curing after vacuumizing is finished, wherein the curing procedure is as follows: 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h +240 ℃/2h, and finally the polyimide/cyanate composite material is obtained.
Example 4
(1) The polyimide was prepared in the same manner as in example 1.
(2) And preparing carbon balls: glucose (9 g) was dissolved in 100mL of deionized water to form a clear solution, which was then transferred to an autoclave and reacted at 180 ℃ for 12h. The resulting dark brown product was collected by centrifugation at 5000rpm/min and then rinsed twice with deionized water and absolute ethanol in that order. And then drying the mixture at 80 ℃ for 12h to obtain the carbon spheres.
(3) Mesoporous SiO 2 The preparation of (1): a mixed solvent composed of absolute ethanol (100 ml) and deionized water (50 ml) was prepared, and the carbon spheres (0.5 g) obtained in step (2) were added to the solvent to obtain a suspension (carbon sphere suspension) which was then stirred at 400rpm/min for 0.5h. CTAB (0.5 g) was added to the carbon sphere suspension and stirring was continued for 0.5h to obtain another suspension (carbon sphere-CTAB suspension), and 1.4mL of aqueous ammonia was added. After that, TEOS (2 ml) was slowly dropped into the carbon sphere-CTAB suspension while stirring at 400rpm/min for 12h. The suspension after the reaction was subjected to two cycles, i.e., centrifugation (5000 rpm/min)/washing/redispersion, and the resulting precipitate was collected in anhydrous ethanol, and then oven-dried at 80 ℃ for 12 hours. Finally, sintering the prepared product in air at 550 ℃ for 4h to obtain mesoporous SiO 2 。
(4) Vinyl mesoporous SiO 2 The preparation of (1): 2mL of vinyltrimethoxysilane and 6mL of deionized water solution are prepared and are kept stand for 2 hours to obtain vinyltrimethylAdding 0.5g of mesoporous SiO prepared in the step (3) into a 100mL round-bottom flask 2 50ml of toluene is ultrasonically treated for 30min, the vinyltrimethoxysilane solution is added, the mixture is stirred for 18h at 80 ℃ until the mixture becomes gel-like, the obtained gel is washed to be neutral, and the gel is dried for 12h under vacuum at 80 ℃ to obtain the vinyl mesoporous SiO 2 。
(5) And preparing a polyimide/cyanate ester resin prepolymer: at 100 ℃, 1g of polyimide is added into a beaker filled with 10g of cyanate ester, and after the polyimide is melted, the mixture is stirred for 30min to obtain uniform transparent liquid, thus obtaining the polyimide/cyanate ester resin prepolymer.
(6) Vinyl mesoporous SiO 2 Preparation of polyimide-cyanate ester resin prepolymer: 0.1g of the vinyl mesoporous SiO obtained in (4) 2 Adding the mixture into the polyimide/cyanate ester resin prepolymer obtained in the step (5), magnetically stirring the mixture for 1 hour, and adding a proper amount of dibutyltin dilaurate to obtain vinyl mesoporous SiO 2 Polyimide-cyanate ester resin prepolymer.
(7) Vinyl mesoporous SiO 2 Preparation of polyimide-cyanate resin composite material: the vinyl mesoporous SiO obtained in the step (6) 2 Injecting the polyimide-cyanate ester resin prepolymer into an aluminum mould while the polyimide-cyanate ester resin prepolymer is hot, then transferring the polyimide-cyanate ester resin prepolymer into a vacuum oven, vacuumizing the vacuum oven for 30min at the temperature of 100 ℃, and transferring the polyimide-cyanate ester resin prepolymer into an air-blowing drying oven for curing after vacuumizing is finished, wherein the curing procedure comprises the following steps: 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h +240 ℃/2h, and finally the vinyl mesoporous SiO is obtained 2 A polyimide-cyanate ester resin nano composite material.
Example 5
(1) Preparation of polyimide in the same manner as in example 1, mesoporous SiO vinyl 2 The preparation method of (D) is the same as in example 4.
(2) And preparing a polyimide/cyanate ester resin prepolymer: at 100 ℃, 1g of polyimide is added into a beaker filled with 10g of cyanate ester, and after the polyimide is melted, the mixture is stirred for 30min to obtain uniform transparent liquid, thus obtaining the polyimide/cyanate ester resin prepolymer.
(3) Vinyl mesoporous SiO 2 Polyimide-cyanate ester resinPreparation of a lipid prepolymer: 0.5g of vinyl mesoporous SiO 2 Adding the mixture into the polyimide/cyanate ester resin prepolymer obtained in the step (2), magnetically stirring for 1 hour, and adding a proper amount of dibutyltin dilaurate to obtain vinyl mesoporous SiO 2 A polyimide-cyanate ester resin prepolymer.
(4) Vinyl mesoporous SiO 2 Preparation of polyimide-cyanate resin composite material: the vinyl mesoporous SiO obtained in the step (3) 2 Injecting the polyimide-cyanate ester resin prepolymer into an aluminum mould while the prepolymer is hot, then transferring the prepolymer into a vacuum oven, vacuumizing the vacuum oven for 30min at 100 ℃, transferring the prepolymer into a forced air drying oven for curing after vacuumizing is finished, wherein the curing procedure is as follows: 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h +240 ℃/2h, and finally vinyl mesoporous SiO is obtained 2 A polyimide-cyanate ester resin nano composite material.
Example 6
(1) Preparation of polyimide in the same manner as in example 1, mesoporous SiO vinyl 2 The preparation method of (2) is the same as example 4.
(2) And preparing a polyimide/cyanate ester resin prepolymer: at 100 ℃, 1g of polyimide is added into a beaker filled with 10g of cyanate ester, and after the polyimide is melted, the mixture is stirred for 30min to obtain uniform transparent liquid, thus obtaining the polyimide/cyanate ester resin prepolymer.
(3) Vinyl mesoporous SiO 2 Preparation of polyimide-cyanate ester resin prepolymer: 1.0g of vinyl mesoporous SiO 2 Adding the mixture into the polyimide/cyanate ester resin prepolymer obtained in the step (2), magnetically stirring for 1 hour, and adding a proper amount of dibutyltin dilaurate to obtain vinyl mesoporous SiO 2 Polyimide-cyanate ester resin prepolymer.
(4) Vinyl mesoporous SiO 2 Preparation of polyimide-cyanate resin composite material: the vinyl mesoporous SiO obtained in the step (3) 2 Injecting the polyimide-cyanate ester resin prepolymer into an aluminum mould while the prepolymer is hot, then transferring the prepolymer into a vacuum oven, vacuumizing the vacuum oven for 30min at 100 ℃, transferring the prepolymer into a forced air drying oven for curing after vacuumizing is finished, wherein the curing procedure is as follows: 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h +240 ℃/2h to finally obtain vinyl mesoporous SiO 2 A polyimide-cyanate ester resin nano composite material.
TABLE 1. Cyanate ester, polyimide/cyanate ester resin and vinyl mesoporous SiO 2 TGA data summary of polyimide-cyanate ester resin composite
TABLE 2 cyanate ester, polyimide/cyanate ester resin and vinyl mesoporous SiO 2 Dielectric property data (1 MHz) of polyimide-cyanate ester resin composite material
TABLE 3 cyanate ester, polyimide/cyanate ester resin and vinyl mesoporous SiO 2 Summary of mechanical Properties of polyimide-cyanate ester resin composites
TABLE 4 cyanate ester, polyimide/cyanate ester resin and vinyl mesoporous SiO 2 Cure peak temperature schedule for polyimide-cyanate ester resin composites
The results of the test show that: as shown in the attached drawing, the prepared mesoporous SiO 2 The structure is regular, and the hollow cavity with the diameter of about 500nm is formed; with the increase of the content of polyimide, the rough fracture surface of the polyimide/cyanate ester resin is beneficial to improving the toughness, but when the content of polyimide is 15%, the appearance of phase separation is beneficial to improving the toughness, but the dielectric property is reduced, so that the content of polyimide is preferably 10%. Such asTables 1, 2, 3, and 4 show that the vinyl mesoporous SiO of the present invention 2 Compared with pure cyanate ester resin, the carbon residue rate of the polyimide-cyanate ester resin composite material at 800 ℃ is obviously increased, which is attributed to SiO 2 The polyimide-cyanate resin contains an inorganic Si-O-Si framework, and has better thermal stability at high temperature. According to the dielectric property data, the mesoporous SiO is shown due to vinyl 2 The introduction of the porous structure enables air to exist in the polymer and a chain with large free volume in the polyimide, thereby obviously reducing the dielectric constant and the dielectric loss. When vinyl mesoporous SiO 2 When the amount of (A) is 5%, the dielectric constant is decreased from 3.26 to 2.65 and the dielectric loss is decreased from 0.0138 to 0.0062 at a frequency of 1 MHz. Thus, vinyl mesoporous SiO 2 The addition of (2) greatly improves the dielectric property of the resin system. According to the impact strength data, IPN and vinyl mesoporous SiO formed by polyimide and cyanate ester are shown 2 When the vinyl group is present, the SiO is mesoporous 2 When the addition amount is 5%, the impact strength, the bending strength and the tensile strength are also greatly improved, and in addition, the introduction of the polyimide and the vinyl mesoporous silica can greatly reduce the curing temperature of the cyanate ester. The invention is not limited to the contents of the embodiments. It will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and any changes and modifications made are within the protective scope of the present invention.
Claims (10)
1. Vinyl mesoporous SiO 2 The polyimide-cyanate ester resin nano composite material is characterized by comprising 100 parts by weight of cyanate ester, 5-10 parts by weight of polyimide and 1-10 parts by weight of vinyl mesoporous SiO 2 Nano material, 0.2-0.6 part of catalyst; the vinyl mesoporous SiO 2 The nano material is vinyl mesoporous SiO which is modified by vinyl trimethoxy silane by taking carbon spheres as a template and tetraethoxysilane as a silicon source material 2 (ii) a The matrix resin is a copolymer of cyanate resin and polyimide resin.
2. According to claim 1The vinyl mesoporous SiO 2 The polyimide-cyanate ester resin nano composite material is characterized in that the mesoporous SiO is 2 The nano material is vinyl mesoporous SiO which is modified by vinyl trimethoxy silane and takes a carbon sphere prepared by glucose hydrothermal as a template and tetraethoxysilane as a silicon source material 2 。
3. The vinyl mesoporous SiO of claim 1 2 The polyimide-cyanate ester resin nano composite material is characterized in that the cyanate ester resin is one of bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin and bisphenol F type cyanate ester resin.
4. The vinyl mesoporous SiO of claim 1 2 The polyimide-cyanate ester resin nano composite material is prepared from polyimide, wherein an anhydride monomer of the polyimide is one or a mixture of more of pyromellitic dianhydride, dimethylketotetracarboxylic dianhydride, 3, 4-biphenyl tetracarboxylic anhydride, triphenyl diether tetracarboxylic dianhydride and biphenyl diether dianhydride; the polyamine is one or more of p-phenylenediamine, 4-diphenyl sulfone diamine, m-phenylenediamine, 3 '-diamino diphenyl sulfone and 4,4' -diamino benzene.
5. The vinyl mesoporous SiO of claim 1 2 The polyimide-cyanate ester resin nano composite material is characterized in that the catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate or dibutyltin didodecyl sulfenyl.
6. The vinyl mesoporous SiO of claim 1 2 The polyimide-cyanate ester resin nano composite material is characterized in that the mass of the cyanate ester resin is 100 parts, and the mass of the polyimide is 5-10 parts.
7. The vinyl mesoporous SiO of claim 1 2 The polyimide-cyanate ester resin nano composite material is characterized in that the vinyl mesoporous SiO 2 Nano material and cyanic acidThe mass ratio of the ester resin is 0.01 to 0.1.
8. A method for modifying cyanate ester by vinyl mesoporous silica and polyimide is characterized by comprising the following steps:
s01, preparing a glucose aqueous solution with a certain concentration into a reaction kettle, carrying out hydrothermal reaction for 12 hours at 180 ℃, and washing to obtain the glucose carbon spheres.
S02, preparing a carbon sphere suspension of carbon spheres, deionized water and ethanol according to a certain proportion, adding a certain amount of CTAB, ammonia water and tetraethoxysilane, stirring for 12 hours to obtain a silicon dioxide suspension, washing and drying for 12 hours, and calcining for 4 hours at 550 ℃ in a muffle furnace to obtain mesoporous silicon dioxide powder.
S03 preparing vinyltrimethoxysilane and a deionized water solution according to a certain proportion, reacting for a period of time, and adding the solution to the mesoporous SiO subjected to ultrasonic treatment 2 And in the toluene mixed solution, condensing and refluxing for 18h at the temperature of 80 ℃, washing and drying after the reaction to obtain the vinyl mesoporous SiO 2 。
S04, weighing the cyanate ester resin and the polyimide according to the proportion, heating to melt, and stirring until the mixture is uniform and transparent to obtain the prepolymer resin.
S05, heating the prepolymer grease to 100 ℃, and adding vinyl mesoporous SiO 2 Adding appropriate amount of dibutyltin dilaurate serving as a catalyst into the nano material, and magnetically stirring at the temperature to obtain vinyl mesoporous SiO 2 The SiO is prepared from polyimide-cyanate ester resin prepolymer 2 1-10% of CE, and 0.2-0.6% of dibutyltin dilaurate.
S06, injecting the prepolymer into a mold, placing the mold in a vacuum oven, removing air bubbles at 100 ℃, and then transferring the mold to a forced air drying oven for curing treatment to obtain vinyl mesoporous SiO 2 A polyimide-cyanate ester resin nano composite material.
9. The vinyl mesoporous SiO of claim 6 2 The polyimide-cyanate ester resin nano composite material is characterized in that the vinyl mesoporous SiO is 2 The nanometer material is glucose hydrothermal charcoalThe ball is an inorganic nano particle of which the template is modified by vinyl trimethoxy silane.
10. The vinyl mesoporous SiO of claim 6 2 The polyimide-cyanate ester resin nano composite material is characterized in that the curing treatment temperature is 150-240 ℃, and the curing time is 8-13 h.
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