CN114106267A - Thermosetting resin composition containing styrene compound, preparation method and application thereof - Google Patents
Thermosetting resin composition containing styrene compound, preparation method and application thereof Download PDFInfo
- Publication number
- CN114106267A CN114106267A CN202111442676.2A CN202111442676A CN114106267A CN 114106267 A CN114106267 A CN 114106267A CN 202111442676 A CN202111442676 A CN 202111442676A CN 114106267 A CN114106267 A CN 114106267A
- Authority
- CN
- China
- Prior art keywords
- resin composition
- thermosetting resin
- parts
- compound
- divinyl
- Prior art date
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- Granted
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- -1 styrene compound Chemical class 0.000 title claims abstract description 65
- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 16
- 125000002015 acyclic group Chemical class 0.000 claims abstract description 12
- 150000001993 dienes Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims abstract 2
- 239000003999 initiator Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 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 24
- 150000003254 radicals Chemical class 0.000 claims description 23
- 239000003063 flame retardant Substances 0.000 claims description 19
- 239000011256 inorganic filler Substances 0.000 claims description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000005227 gel permeation chromatography Methods 0.000 claims description 12
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 11
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- ZXLAFQNTMMFLSA-UHFFFAOYSA-N 1-ethenyl-4-[2-(4-ethenylphenyl)ethyl]benzene Chemical compound C1=CC(C=C)=CC=C1CCC1=CC=C(C=C)C=C1 ZXLAFQNTMMFLSA-UHFFFAOYSA-N 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 claims description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 3
- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 claims description 3
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- OOVQLEHBRDIXDZ-UHFFFAOYSA-N 7-ethenylbicyclo[4.2.0]octa-1,3,5-triene Chemical compound C1=CC=C2C(C=C)CC2=C1 OOVQLEHBRDIXDZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 3
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- UILHJQOGYLLFNJ-UHFFFAOYSA-N methyl prop-2-enoate silane Chemical compound [SiH4].COC(C=C)=O UILHJQOGYLLFNJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 238000004260 weight control Methods 0.000 claims description 3
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229920001890 Novodur Polymers 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003365 glass fiber Substances 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 12
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000008054 signal transmission Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- DALNRYLBTOJSOH-UHFFFAOYSA-N 3,3,5,7,7-pentamethyl-1,2,4-trioxepane Chemical compound CC1CC(C)(C)OOC(C)(C)O1 DALNRYLBTOJSOH-UHFFFAOYSA-N 0.000 description 2
- 241001521809 Acoma Species 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to a thermosetting resin composition containing a styrene compound, which comprises the following raw material components in parts by weight: 15-50 parts of unsaturated triblock copolymer, 35-75 parts of polyfunctional styrene compound, 5-25 parts of auxiliary crosslinking agent and 0.2-3 parts of free radical polymerization initiator; the unsaturated triblock copolymer is an a-B-a type block structure in which the a blocks are poly (alkenyl arene) polymers comprising monoalkenyl arene units and the B blocks are non-hydrogenated poly (acyclic conjugated diene) polymers comprising polymerized units of at least one acyclic conjugated diene. The resin composition has low dielectric constant and low dielectric loss, small change rate of dielectric loss after moisture absorption, low water absorption, high thermal stability and good reliability, and the cured product of the thermosetting resin composition has a dielectric loss factor of less than 0.0014 at 10GHz, so that the thermosetting resin composition can be used for manufacturing a multilayer printed circuit board with excellent processability, low dielectric property and high reliability.
Description
Technical Field
The invention relates to the technical field of resin compositions, in particular to a thermosetting resin composition containing a styrene compound, and a preparation method and application thereof.
Background
With the rapid development of electronic technology, high-frequency signal transmission is required for large-capacity computer systems and electronic products such as communication base stations, servers, storage devices, and the like. However, the higher the signal transmission frequency, the greater the loss of the electric signal transmission loss, the lower the transmission signal loss, and the lower the reliability of the signal transmission, and therefore, the dielectric dissipation factor of the substrate must be further reduced at high frequency and high transmission rate. The low dielectric resin material is a key material for high frequency high transmission devices in order to meet the future demand for high speed information transmission.
Currently, a printed circuit board uses polyphenylene oxide (PPO, or called as a polyphenylene oxide resin) to reduce the dielectric constant Dk and dielectric loss factor Df of a substrate, and is used in medium and high-end copper clad laminates and printed circuit boards due to its low dielectric loss and good heat resistance and environmental reliability, but the dielectric loss is not sufficient to cope with at higher frequencies. Therefore, further development of resin compositions having a lower dielectric dissipation factor Df is a positive development goal in the current industry.
Disclosure of Invention
The present invention is directed to solving the above problems and to providing a thermosetting resin composition containing a styrenic compound, a method for preparing the same, and use thereof.
The thermosetting resin composition has the advantages of low dielectric constant, low dielectric loss, small change rate of dielectric loss after moisture absorption, low water absorption, high thermal stability and good reliability. In addition, the thermosetting resin composition avoids occurrence of macro phase separation of the resin system, and achieves excellent processability, low dielectric property, and high heat resistance.
The purpose of the invention can be realized by the following technical scheme:
a styrene compound-containing thermosetting resin composition comprising the following components: an unsaturated triblock copolymer (a), a polyfunctional styrene compound (b), an auxiliary crosslinking agent (c), and a radical polymerization initiator (d), wherein the cured product of the thermosetting resin composition has a dielectric dissipation factor at 10GHz of 0.0014 or less.
Further, the composition comprises the following components in parts by mass: 15-50 parts of unsaturated triblock copolymer (a), 35-75 parts of polyfunctional styrene compound (b), 5-25 parts of auxiliary crosslinking agent (c) and 0.2-3 parts of free radical polymerization initiator (d).
The unsaturated triblock copolymer has a number average molecular weight Mn of 5,000-50,000g/mol as determined by Gel Permeation Chromatography (GPC), has narrow molecular weight control, and has a ratio PDI of weight average molecular weight Mw to number average molecular weight Mn of not more than 1.20, wherein the poly (alkenyl arene) structural units account for 30-75% of the total mass.
The unsaturated triblock copolymers are a-B-a type block structures where the a block is a poly (alkenyl arene) polymer comprising at least high Tg mono alkenyl arene units with a Tg >100 ℃ or >125 ℃, where the a block GPC peak molecular weight Mp is a poly (alkenyl arene) homopolymer of less than 3,5000g/mol, examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, a-methylstyrene, p-a-dimethylstyrene, vinyl-benzocyclobutene, vinylbiphenyl, adamantyl styrene, 1-diphenyl-ethylene, and benzofullerene;
wherein the B block is a non-hydrogenated poly (acyclic conjugated diene) polymer comprising polymerized units of at least one acyclic conjugated diene; the polymer has a high-reactivity structural unit, and the side group has an unsaturated double bond structure; the GPC peak molecular weight Mp of the B block is greater than 3,000g/mol and less than 3,0000 g/mol. Wherein the poly (acyclic conjugated diene) polymer is obtained by anionic polymerization and has a highly selective 1, 2-vinyl structural unit, wherein the molar proportion of the 1, 2-vinyl polyolefin structure in the entire B block is more than 85%, and further the proportion of the 1, 2-vinyl polyolefin structure is more than 90%. The non-hydrogenated poly (acyclic conjugated diene) polymer structure may be exemplified by 1, 2-polybutadiene or 1, 2-polyisoprene.
The molecular structure of the multifunctional styrene compound (B) is shown as the following formula (1),
wherein R represents a hydrocarbon skeleton, R1Represents a C1-C20 hydrocarbon group, R2，R3，R4Represents a hydrogen atom or a hydrocarbon group of C1-C6, R2，R3，R4The same or different, m is an integer of 1 to 4, and n is an integer of 2 or more.
The polyfunctional styrene compound is a vinyl compound having a number average molecular weight of 1000g/mol or less, preferably 170g/mol or more and 800g/mol or less. In the present invention, the small molecule vinyl compound may be exemplified by the following chemical structures but not limited to p, p ' -divinyl-1, 2-diphenylethane (p, p ' -BVPE), m ' -divinyl-1, 2-diphenylethane (m, m ' -BVPE), m, p ' -divinyl-1, 2-diphenylethane (m, p ' -BVPE), p ' -divinyl-1, 2-diphenylmethane (p, p ' -BVPM), m ' -divinyl-1, 2-diphenylmethane (m, m ' -BVPM), m, p ' -divinyl-1, 2-diphenylmethane (m, p ' -BVPM), and p, p ' -divinyl-1, one or more kinds of isomers such as 2-diphenylpropane (p, p ' -BVPP), m ' -divinyl-1, 2-diphenylpropane (m, m ' -BVPP), m, p ' -divinyl-1, 2-diphenylpropane (m, p ' -BVPP), and the like. Wherein p, p 'represents the para position of the benzene ring, and m, m' represents the meta position of the benzene ring. Further, the polyfunctional styrene compound is more preferable and may be p, p '-divinyl-1, 2-diphenylethane (p, p' -BVPE).
The auxiliary crosslinking agent (c) comprises one or more of styrene, divinyl benzene, triallyl isocyanurate, acrylate compounds, methacrylate compounds or maleimide resin.
Furthermore, the auxiliary crosslinking agent contains an unsaturated double bond structure, and can form a curable crosslinking structure with the unsaturated triblock copolymer, the polyfunctional styrene compound and the like, so that the mechanical strength and the glass transition temperature of the material are improved, the bonding strength of the resin and the copper foil is improved, and the resin flowability is improved.
The radical polymerization initiator (d) includes a first radical initiator d1 having a one-hour half-life temperature of 80-120 ℃ and a second radical initiator d2 having a one-hour half-life temperature of 130-170 ℃. The total mass of the free radical polymerization initiator accounts for 0.2 to 3 parts by mass of the resin composition.
The first and second radical initiators can each initiate a crosslinking reaction of unsaturated double bonds in the resin composition at different temperatures (i.e., above the first and second crosslinking temperatures, respectively). Thus, the resin composition is partially crosslinked at about a first crosslinking temperature (i.e., a relatively low temperature of 80-120 ℃) and is further crosslinked at about a second crosslinking temperature (i.e., a relatively high temperature of 130-170 ℃). Thus, the first free radical initiator may be characterized as a relatively low temperature free radical initiator. In contrast, the second free radical initiator may be characterized as a relatively high temperature free radical initiator.
The resin composition is subjected to partial crosslinking reaction at a lower temperature of 80-120 ℃ to form a prepreg, still has good reactivity and fluidity, and the partially reacted unsaturated double bonds can be further cured to form a substrate material only at a temperature higher than the second crosslinking temperature, namely 130-170 ℃, so that the prepreg formed at the first crosslinking temperature has good stability and cannot excessively react to cause the problem of poor hot-pressing curing production.
The first and second free radical initiators may each be an organic peroxide or an azo compound, the first and second free radical initiators being different from each other. Preferably, the first free radical initiator may be dibenzoyl peroxide or 1, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane and the second free radical initiator may be di-t-butyl peroxide, cumyl hydroperoxide, t-butyl hydroperoxide, or 3,3,5,7, 7-pentamethyl-1, 2, 4-trioxepane.
Further, the composition further comprises a flame retardant (e) and an inorganic filler (f); the concrete content is as follows: 10-40 parts of flame retardant (e) and 50-100 parts of inorganic filler (f).
The flame retardant comprises one or more of decabromodiphenylethane, decabromodiphenylether, octabromodiphenylether, ethylene bis-tetrabromophthalimide and tris (tribromophenyl) isocyanurate.
The inorganic filler is low dielectric synthetic spherical silica filler, the filler is spherical silica filler with the surface treated by vinyl or allyl or (methyl) acrylate silane coupling agent, and the dielectric loss of the spherical silica filler is less than 0.0014 at the frequency of 10 GHz; the average grain diameter D50 of the flame retardant and the inorganic filler is selected to be 0.5-5 μm.
The production method of the prepreg comprises the following steps: soaking a fabric into the thermosetting resin composition, then soaking the fabric into low-dielectric electronic grade glass fiber cloth, and heating and drying the fabric at a first crosslinking temperature of 80-120 ℃ to obtain a prepreg; the low-dielectric electronic-grade glass fiber cloth is formed by alternately weaving warps and wefts, wherein the warps and the wefts are all made of monofilaments, the whole electronic-grade glass fiber cloth is in a flattened structure, and the warps and the wefts are all made of low-dielectric-constant fiber lines.
Manufacturing a metal foil-clad laminated board, wherein the laminated board is prepared by overlapping a conductive foil and the prepreg; the average surface roughness of the conductive foil is less than 1.5 mu m, and the surface of the conductive foil is treated by a silane coupling agent.
And manufacturing a multilayer printed circuit board by matching the prepreg and the metal foil-clad laminate, wherein the loss factor Df of the multilayer printed circuit board at 10GHz is less than or equal to 0.0014, and the dielectric constant Dk of the multilayer printed circuit board at 10GHz is less than 3.3.
Compared with the prior art, the invention has the following advantages:
(1) the invention uses a novel unsaturated triblock polymer, the designed molecular structure has good resin system compatibility, and the midblock has a regular 1, 2-olefin block structure, so that the invention has good reactivity and low dielectric property;
(2) the used polyfunctional styrene compound has a whole alkane skeleton structure with a plurality of styryl groups and a regular rigid skeleton structure, and a cured product of the polyfunctional styrene compound has an extremely low dielectric loss tangent value in terms of dielectric loss, so that the aim of the low-dielectric-loss thermosetting resin composition is fulfilled; meanwhile, the rigid structure of the material enables the material to have high glass transition temperature and ultrahigh heat resistance, and the thermal stability and reliability of the cured base material can be improved.
(3) The polymerization reaction of the resin composition is controlled by the high-low temperature free radical initiator, namely, the first free radical initiator and the second free radical initiator can respectively initiate the crosslinking reaction of unsaturated double bonds in the resin composition at different temperatures (respectively higher than the first crosslinking temperature and the second crosslinking temperature).
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
According to one aspect of the present invention, the present invention provides a styrene compound-containing thermosetting resin composition comprising the following components in parts by mass: 15-50 parts of unsaturated triblock copolymer (a), 35-75 parts of polyfunctional styrene compound (b), 5-25 parts of auxiliary crosslinking agent (c) and 0.2-1 part of free radical polymerization initiator (d); 10-40 parts of flame retardant (e) and 50-100 parts of inorganic filler (f).
Wherein the unsaturated triblock copolymer has a number average molecular weight Mn of 5,000-50,000g/mol as determined by gel permeation chromatography GPC, has narrow molecular weight control, and has a ratio PDI of weight average molecular weight Mw to number average molecular weight Mn of not more than 1.20, wherein the poly (alkenyl arene) structural units account for 30-75% of the total mass thereof.
The unsaturated triblock copolymer is an a-B-a type block structure, the a block being a poly (alkenyl arene) polymer comprising mono alkenyl arene units, the B block being a non-hydrogenated poly (acyclic conjugated diene) polymer comprising polymerized units of at least one acyclic conjugated diene. The a block is a poly (alkenyl arene) polymer comprising at least high Tg mono alkenyl arene units having a Tg >100 ℃ or >125 ℃, a poly (alkenyl arene) homopolymer having a GPC peak molecular weight Mp of the a block of less than 35,000 g/mol; the B block has a highly reactive structural unit, the pendant group has an unsaturated double bond structure, the poly (acyclic conjugated diene) polymer is obtained by anionic polymerization, and has a highly selective 1, 2-vinyl structural unit, wherein the molar proportion of the 1, 2-vinyl polyolefin structure to the whole B block is more than 85%, and the GPC peak molecular weight Mp of the B block is more than 3,000g/mol and less than 30,000 g/mol. For example, the a block comprises one or more of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α -methylstyrene, p- α -dimethylstyrene, vinyl-benzocyclobutene, vinylbiphenyl, adamantyl styrene, 1-diphenyl-ethylene, or benzofullerene; the B block comprises one or two of 1, 2-polybutadiene or 1, 2-polyisoprene.
The molecular structure of the polyfunctional styrene compound (b) is represented by the following formula (1):
wherein R represents a hydrocarbon skeleton, R1Represents a C1-C20 hydrocarbon group, R2，R3，R4Represents a hydrogen atom or a hydrocarbon group of C1-C6, R2，R3，R4May be the same or different, and m is 1A vinyl compound having an integer of-4, n is an integer of 2 or more, and the number average molecular weight of the polyfunctional styrene compound (b) is 1000g/mol or less.
For example, the vinyl compound includes, but is not limited to, any one or more of p, p ' -divinyl-1, 2-diphenylethane, m ' -divinyl-1, 2-diphenylethane, m, p ' -divinyl-1, 2-diphenylethane, p ' -divinyl-1, 2-diphenylmethane, m ' -divinyl-1, 2-diphenylmethane, m, p ' -divinyl-1, 2-diphenylmethane and p, p ' -divinyl-1, 2-diphenylpropane, m ' -divinyl-1, 2-diphenylpropane, m, p ' -divinyl-1, 2-diphenylpropane, wherein p, p 'represents the para position of the benzene ring, and m, m' represents the meta position of the benzene ring.
For example, the co-crosslinking agent (c) includes one or more of styrene, divinylbenzene, triallyl isocyanurate, an acrylate compound, a methacrylate compound, or a maleimide resin;
the free radical polymerization initiator (d) comprises a first free radical initiator (d1) with the one-hour half-life temperature of 80-120 ℃ and a second free radical initiator (d2) with the one-hour half-life temperature of 130-170 ℃, and the mass sum of the free radical polymerization initiators accounts for 0.2-1 part of the resin composition; the first free radical initiator and the second free radical initiator are each an organic peroxide or an azo compound. For example, the first free radical initiator may be dibenzoyl peroxide or 1, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane and the second free radical initiator may be di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxide, or 3,3,5,7, 7-pentamethyl-1, 2, 4-trioxepane.
The thermosetting composition also comprises a flame retardant (e) and an inorganic filler (f), and the specific contents are as follows: 10-40 parts of flame retardant (e), and 50-100 parts of inorganic filler (f); for example, the flame retardant comprises one or more of decabromodiphenyl ethane, decabromodiphenyl ether, octabromodiphenyl ether, ethylene bistetrabromophthalimide and tris (tribromophenyl) isocyanurate; the inorganic filler is a low-dielectric synthetic spherical silica filler, the filler is a spherical silica filler the surface of which is treated by a vinyl or allyl or (methyl) acrylate silane coupling agent, and the dielectric loss of the spherical silica filler is less than 0.0014 at the frequency of 10 GHz; the average particle diameter D50 of the flame retardant and the inorganic filler is selected in the range of 0.5 to 5 μm.
The preparation method of the thermosetting resin composition comprises the steps of dissolving the unsaturated triblock copolymer (a) and the polyfunctional styrene compound (b) in a solvent, adding the auxiliary crosslinking agent (c), mixing and stirring uniformly, adding the free radical polymerization initiator (d), dispersing to obtain the thermosetting resin composition containing the styrene compound, and adding the flame retardant and/or the inorganic filler between the addition of the free radical polymerization initiator (d).
The prepared thermosetting resin composition is used for manufacturing prepregs, metal foil-clad laminates and multilayer printed circuit boards.
When the prepreg is manufactured, the fabric is soaked in the thermosetting resin composition, then the fabric is soaked in the low-dielectric electronic grade glass fiber cloth and then heated and dried to obtain the prepreg; the low-dielectric electronic-grade glass fiber cloth is formed by alternately weaving warps and wefts, the warps and the wefts are all made of monofilaments, the whole electronic-grade glass fiber cloth is in a flat structure, and the warps and the wefts are all made of low-dielectric-constant fiber lines.
Manufacturing a metal foil-clad laminate, which is prepared by overlapping a conductive foil with a prepreg; the average surface roughness of the conductive foil is less than 1.5 mu m, and the surface of the conductive foil is treated by a silane coupling agent.
And manufacturing a multilayer printed circuit board, wherein the multilayer printed circuit board is manufactured by matching a prepreg and the metal foil-clad laminate, the loss factor Df of the multilayer printed circuit board at 10GHz is less than or equal to 0.0014, and the dielectric constant Dk of the multilayer printed circuit board at 10GHz is less than 3.3.
The following are specific examples of examples 1 to 5 and comparative examples 1 to 3
Examples 1 to 3
A pre-dip of the thermosetting resin composition was prepared according to the formulation listed in Table 1: unsaturated triblock polymer SBS-A (Mn 26,000g/mol, PDI 1.18, St/Bd/St 25/50/25, 1, 2-vinyl content 92%, Nippon CaodA corporation) and polyfunctional styrene compound BVPE (p, p' -divinyl-1, 2-diphenylethane, Hippon Seisakuki Co., Ltd.) were dissolved in A toluene solvent, and then A co-crosslinking agent TAIC (triallyl isocyanurate, Nippon Kasei Co., Ltd.) was added thereto, and the mixture was mixed and stirred uniformly, and then flame retardant SAYTEX8010 (decabromodiphenylethane, D50 particle diameter 3.5um, Yabao chemical Co., Ltd.) and inorganic filler SE00XX (spherical silicA filler, D50 particle diameter 2.5um, brocade silicon material Co., Ltd.) were added thereto, and dispersed uniformly by A high-speed rotary mixer, and then low-temperature radical polymerization initiator BPO (dibenzoyl peroxide was added, the one-hour half-life temperature is 95 ℃, and the temperature of the one-hour half-life is 137 ℃, and the pre-impregnation liquid containing the thermosetting resin composition is obtained after mixing and stirring of an ABC chemical company and a high-temperature free radical polymerization initiator DCP (dicumyl peroxide).
Soaking a glass fiber fabric (1078L2 Low dielectric glass fiber cloth, manufactured by AST company) in the pre-dip solution of the thermosetting resin composition, drying at 120 deg.C for 5min, and removing toluene solvent to obtain a prepreg; then, the prepreg was laminated by 6 sheets, sandwiched between Hoz HVLP3 copper foils (Rz. about.0.8 um, Mitsui copper foil Co., Ltd.) on the upper and lower sides, and then hot-pressed and cured at 190 ℃/120min at a temperature rise rate of 2 ℃/min and a pressing pressure of 4MPa from room temperature to obtain a metal-clad laminate.
Examples 4 to 5
A pre-dip of the thermosetting resin composition was prepared according to the formulation listed in Table 1: unsaturated triblock polymer SBS-B (Mn 8,440g/mol, PDI 1.07, St/Bd/St 15/70/15, 1, 2-vinyl content 94%, Nippon Caoda corporation) and polyfunctional styrene compound BVPE (p, p' -divinyl-1, 2-diphenylethane, Hill. science and technology Co., Ltd.) were dissolved in toluene solvent, then co-crosslinking agent TAIC (triallyl isocyanurate, Nippon chemical Co., Ltd.) was added thereto, mixed and stirred uniformly, flame retardant SAYTEX8010 (decabromodiphenylethane, D50 particle diameter 3.5um, Yabao chemical Co., Ltd., USA) and inorganic filler SE00XX (spherical silica filler, D50 particle diameter 2.5um, brocade silicon material Co., Ltd.) were added thereto, dispersed uniformly by a high speed rotary mixer, low temperature radical polymerization initiator BPO (dibenzoyl peroxide) was added thereto, the one-hour half-life temperature is 95 ℃, and the temperature of the one-hour half-life is 137 ℃, and the pre-impregnation liquid containing the thermosetting resin composition is obtained after mixing and stirring of an ABC chemical company and a high-temperature free radical polymerization initiator DCP (dicumyl peroxide).
Soaking a glass fiber fabric (1078L2 Low dielectric glass fiber cloth, manufactured by AST company) in the pre-dip solution of the thermosetting resin composition, drying at 120 deg.C for 4min, and removing toluene solvent to obtain a prepreg; the prepreg was then laminated by 6 sheets, sandwiched between Hoz HVLP3 copper foils (Rz. about.0.8 um, Mitsui copper foil Co., Ltd.) on the top and bottom, and then hot-pressed and cured at 190 ℃/90min at a heating rate of 2.5 ℃/min and a pressing pressure of 3.5MPa from room temperature to prepare a metal-clad laminate.
Comparative example 1
The prepreg of the thermosetting resin composition of comparative example 1 was prepared by dissolving unsaturated polybutadiene B2000(mn2,100g/mol, PDI 1.17, 1, 2-vinyl content 88%, japan caoka co., ltd.) and a polyfunctional styrene compound BVPE (p, p' -divinyl-1, 2-diphenylethane, japan soxhlet technologies) in a toluene solvent, adding a co-crosslinking agent TAIC (triallyl isocyanurate, japan chemicals co., ltd.), mixing and stirring uniformly, adding a flame retardant SAYTEX8010 (decabromodiphenylethane, D50 particle size 3.5um, american yabao chemical ltd.), an inorganic filler SE00XX (spherical silica filler, D50 particle size 2.5um, brocade silicon material ltd.), uniformly dispersing by a high-speed rotary mixer, adding a low-temperature radical polymerization initiator BPO (dibenzoyl peroxide, the one-hour half-life temperature is 95 ℃, and the temperature of the one-hour half-life is 137 ℃, and the pre-impregnation liquid containing the thermosetting resin composition is obtained after mixing and stirring of an ABC chemical company and a high-temperature free radical polymerization initiator DCP (dicumyl peroxide).
Soaking a glass fiber fabric (1078L2 Low dielectric glass fiber cloth, manufactured by AST company) in the pre-dip solution of the thermosetting resin composition, drying at 120 deg.C for 5min, and removing toluene solvent to obtain a prepreg; and then overlapping 6 prepregs, clamping the prepregs by using a Hoz HVLP3 copper foil (Rz-0.8 um, Mitsui copper foil Co., Ltd.) from top to bottom, and carrying out hot-pressing curing molding at the temperature rise rate of 2 ℃/min and the pressure of 4MPa at the temperature of 190 ℃/120min from room temperature to prepare the copper-clad plate.
Comparative example 2
In comparative example 2, only the unsaturated triblock polymer SBS-A was used as the main resin, the polyfunctional styrene compound BVPE was not used, then adding an auxiliary crosslinking agent TAIC (triallyl isocyanurate, Nippon chemical Co., Ltd.), mixing and stirring uniformly, adding a flame retardant SAYTEX8010 (decabromodiphenylethane, D50 particle size of 3.5um, Yabao chemical Co., Ltd., USA), an inorganic filler SE00XX (spherical silica filler, D50 particle size of 2.5um, jin Si material Co., Ltd.), uniformly dispersing by a high-speed rotary mixer, respectively adding a low-temperature radical polymerization initiator BPO (dibenzoyl peroxide, one-hour half-life temperature of 95 ℃, Acoma chemical Co., Ltd.) and a high-temperature radical polymerization initiator DCP (dicumyl peroxide, one-hour half-life temperature of 137 ℃, Acoma chemical Co., Ltd.), mixing and stirring to obtain a pre-impregnation solution containing the thermosetting resin composition; then preparing the copper-clad plate by the same method.
Comparative example 3
The preparation was carried out in addition to example 2, in which a radical polymerization initiator was added only to high-temperature initiator DCP, and the mixture was stirred to obtain a prepreg containing a thermosetting resin composition, a glass fiber fabric (1078L2 low dielectric glass fiber cloth, manufactured by AST) was immersed in the prepreg of the thermosetting resin composition, and the resultant was dried at 120 ℃ for 5 minutes, and the toluene solvent was removed to obtain a prepreg; and then overlapping 6 prepregs, clamping the prepregs by using a Hoz HVLP3 copper foil (Rz-0.8 um, Mitsui copper foil Co., Ltd.) from top to bottom, and carrying out hot-pressing curing molding at the temperature rise rate of 2 ℃/min and the pressure of 4MPa at the temperature of 190 ℃/120min from room temperature to prepare the copper-clad plate.
TABLE 1 EXAMPLES 1 TO 5 AND COMPARATIVE EXAMPLES 1 TO 3 concrete raw material formulas
The performance of the prepared copper-clad plate is tested, the test method is as follows, and the test result is detailed in table 2.
Glass transition temperature (Tg): the measurement was carried out by using a DMA instrument test according to the DMA test method specified in IPC-TM-6502.4.24.4.
Z-axis Coefficient of Thermal Expansion (CTE): measured using a TMA instrument according to the TMA test method specified by IPC-TM-6502.4.24.
Copper foil Peel Strength (PS): measured using Shimadzu tensile machine according to the test method specified by IPC-TM-6502.4.8.
Dielectric constant (Dk) and dielectric loss factor (Df): dielectric constant and dielectric dissipation factor test methods were as specified by IPC-TM-6502.5.5.9.
Autoclave cooking experiment (PCT): the laminates were autoclaved at 120 ℃ and tested according to the test method specified in IPC-TM-6502.6.16.
288 ℃ delamination time (T288): measured using a TMA instrument according to the test method specified in IPC-TM-6502.4.24.1.
Flame retardancy: the test was carried out according to the flammability method of materials as specified in UL-94.
Heat resistance: refers to the property of a substance that can maintain its excellent physical and mechanical properties under the condition of being heated.
Compatibility of the resin system: and (3) observing the microscopic uniformity of the cured resin under SEM by taking the cross section of the base material, wherein if the resin agglomeration phenomenon occurs, the resin is incompatible.
TABLE 2 test results of examples 1 to 5 and comparative examples 1 to 3
As can be seen from Table 2, the copper-clad plates prepared in examples 1 to 5 have good appearances, the loss factor Df at 10GHz is less than or equal to 0.0018, and the dielectric constant Dk at 10GHz is less than 3.3; meanwhile, the laminated board has good thermal performance, and the DMA glass transition temperature is greater than or equal to 225 ℃; the copper clad laminate has a low coefficient of thermal expansion, the CTE is less than 2.35%, the good heat resistance T288 is more than 60min, and the copper clad laminate is tin-dipped for 10s and is not exploded for three times. Further, from the SEM test of the cut sheet of the laminate, it was found that the unsaturated triblock copolymer, the polyfunctional styrene compound and the auxiliary crosslinking agent did not cause phase separation or the like after completion of curing.
From the data of comparative example 1 and example 5, it can be seen that comparative example 1 does not use an unsaturated triblock polymer, but polybutadiene, and both the dielectric constant Dk and the loss tangent Df of the polybutadiene resin are inferior to those of the unsaturated triblock polymer; the polybutadiene causes low peeling strength of the copper foil, the non-layering time is only 32min at 288 ℃, and the copper-clad plate is exploded after tin immersion, which shows that the copper-clad plate is poor in heat resistance; in addition, polybutadiene resin has poor compatibility with polyfunctional styrene compounds, and the problem of resin agglomeration occurs.
As can be seen from the data of comparative example 2, comparative example 2 has no addition of polyfunctional styrene compound, the dielectric constant Dk and the loss factor Df of 10GHz are both obviously deteriorated, and the Tg of the laminated board is obviously reduced due to no polyfunctional styrene compound, only 185 ℃ is needed, the heat resistance is insufficient, the non-lamination time is only 18min at 288 ℃, and the copper-clad board is exploded after tin immersion.
As can be seen from the data of comparative example 3, the initiator of comparative example 3 only uses a high-temperature initiator, and does not use a low-temperature initiator, so that the product has overlarge gummosis and poor appearance, and is difficult to prepare into a product meeting the requirements.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A thermosetting resin composition containing a styrene compound is characterized by comprising the following raw material components in parts by weight: 15-50 parts of unsaturated triblock copolymer (a), 35-75 parts of polyfunctional styrene compound (b), 5-25 parts of auxiliary crosslinking agent (c) and 0.2-3 parts of free radical polymerization initiator (d);
wherein the unsaturated triblock copolymer is an a-B-a type block structure in which the a blocks are poly (alkenyl arene) polymers comprising monoalkenyl arene units and the B blocks are non-hydrogenated poly (acyclic conjugated diene) polymers comprising polymerized units of at least one acyclic conjugated diene.
2. The styrenic resin composition as claimed in claim 1, wherein said unsaturated triblock copolymer has a number average molecular weight Mn of 5,000-50,000g/mol as determined by gel permeation chromatography GPC, has narrow molecular weight control, and has a ratio PDI of weight average molecular weight Mw to number average molecular weight Mn of 1.20 or less, wherein the poly (alkenyl aromatic) structural units account for 30 to 75% of the total mass thereof.
3. The styrenic compound-containing thermosetting resin composition of claim 1, wherein the a block is a poly (alkenyl arene) polymer comprising at least high Tg mono alkenyl arene units having a Tg >100 ℃ or >125 ℃, wherein the a block is a poly (alkenyl arene) homopolymer having a GPC peak molecular weight Mp of less than 35,000 g/mol;
the B block has a highly reactive structural unit, the pendant group has an unsaturated double bond structure, the poly (acyclic conjugated diene) polymer is obtained by anionic polymerization, and has a highly selective 1, 2-vinyl structural unit, wherein the molar proportion of the 1, 2-vinyl polyolefin structure to the whole B block is more than 85%, and the GPC peak molecular weight Mp of the B block is more than 3,000g/mol and less than 30,000 g/mol.
4. The thermosetting resin composition containing a styrenic compound according to claim 3, characterized in that the A block comprises one or more of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α -methylstyrene, p- α -dimethylstyrene, vinyl-benzocyclobutene, vinylbiphenyl, adamantylstyrene, 1-diphenyl-ethylene or benzofullerene; the B block comprises one or two of 1, 2-polybutadiene or 1, 2-polyisoprene.
5. The styrene compound-containing thermosetting resin composition according to claim 1, wherein the molecular structure of the polyfunctional styrene compound (b) is represented by the following formula (1):
wherein R represents a hydrocarbon skeleton, R1Represents a C1-C20 hydrocarbon group, R2，R3，R4Represents a hydrogen atom or a hydrocarbon group of C1-C6, R2，R3，R4The same or different, m is an integer of 1 to 4, and n is an integer of 2 or more.
6. The styrene compound-containing thermosetting resin composition as claimed in claim 5, wherein the polyfunctional styrene compound (b) has a number average molecular weight of 1000g/mol or less,
the vinyl compound includes, but is not limited to, any one or more of p, p ' -divinyl-1, 2-diphenylethane, m ' -divinyl-1, 2-diphenylethane, m, p ' -divinyl-1, 2-diphenylethane, p ' -divinyl-1, 2-diphenylmethane, m ' -divinyl-1, 2-diphenylmethane, m, p ' -divinyl-1, 2-diphenylmethane and p, p ' -divinyl-1, 2-diphenylpropane, m ' -divinyl-1, 2-diphenylpropane, m, p ' -divinyl-1, 2-diphenylpropane, wherein p, p 'represents the para position of the benzene ring, and m, m' represents the meta position of the benzene ring.
7. The thermosetting resin composition containing styrene compound as claimed in claim 5, wherein the co-crosslinking agent (c) comprises one or more of styrene, divinylbenzene, triallylisocyanurate, acrylate compound, methacrylate compound or maleimide resin;
the free radical polymerization initiator (d) comprises a first free radical initiator (d1) with the one-hour half-life temperature of 80-120 ℃ and a second free radical initiator (d2) with the one-hour half-life temperature of 130-170 ℃, and the mass sum of the free radical polymerization initiators accounts for 0.2-3 parts of the resin composition;
the first and second radical initiators are each an organic peroxide or an azo compound.
8. The styrene compound-containing thermosetting resin composition as claimed in claim 1, further comprising a flame retardant (e) and an inorganic filler (f) in the following amounts: 10-40 parts of flame retardant (e), and 50-100 parts of inorganic filler (f);
the flame retardant comprises one or more of decabromodiphenylethane, decabromodiphenylether, octabromodiphenylether, ethylene bis-tetrabromophthalimide and tris (tribromophenyl) isocyanurate;
the inorganic filler is low dielectric synthetic spherical silica filler, the filler is spherical silica filler with the surface treated by vinyl or allyl or (methyl) acrylate silane coupling agent, and the dielectric loss of the spherical silica filler is less than 0.0014 at the frequency of 10 GHz;
the average grain diameter D50 of the flame retardant and the inorganic filler is selected to be 0.5-5 μm.
9. The method for preparing a styrenic resin composition of claim 1, wherein the formulation is prepared by dissolving the unsaturated triblock copolymer (a) and the polyfunctional styrenic compound (b) in a solvent, adding the cross-linking agent (c), mixing and stirring, adding the radical polymerization initiator (d), dispersing to obtain the styrenic resin composition, and adding the flame retardant and/or the inorganic filler between the addition of the radical polymerization initiator (d).
10. The use of the thermosetting resin composition containing a styrenic compound according to claim 1 for producing prepregs, metal-clad laminates and multilayer printed wiring boards.
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