CN116285863A - Composite engineering plastic with low dielectric constant and preparation method thereof - Google Patents
Composite engineering plastic with low dielectric constant and preparation method thereof Download PDFInfo
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- CN116285863A CN116285863A CN202310131031.XA CN202310131031A CN116285863A CN 116285863 A CN116285863 A CN 116285863A CN 202310131031 A CN202310131031 A CN 202310131031A CN 116285863 A CN116285863 A CN 116285863A
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- low dielectric
- engineering plastic
- dielectric constant
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- composite engineering
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- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000001070 adhesive effect Effects 0.000 claims abstract description 36
- 239000000853 adhesive Substances 0.000 claims abstract description 35
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims abstract description 13
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012948 isocyanate Substances 0.000 claims abstract description 3
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 238000001723 curing Methods 0.000 claims description 24
- -1 polydimethylsiloxane Polymers 0.000 claims description 23
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 21
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical class CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 5
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 4
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims 1
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 claims 1
- 229940095102 methyl benzoate Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 7
- 239000003999 initiator Substances 0.000 abstract description 2
- 238000013008 moisture curing Methods 0.000 description 8
- 238000003848 UV Light-Curing Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 2
- BFBBLTGLAVFGCU-UHFFFAOYSA-N C(C(=C)C)(=O)OOCC.NC(=O)N.C=C Chemical compound C(C(=C)C)(=O)OOCC.NC(=O)N.C=C BFBBLTGLAVFGCU-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- MWQBWSPPTQGZII-UHFFFAOYSA-N ethoxy(phenyl)phosphinic acid Chemical compound CCOP(O)(=O)C1=CC=CC=C1 MWQBWSPPTQGZII-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a composite engineering plastic with low dielectric constant, which belongs to the technical field of special plastic preparation, and comprises an engineering plastic body and a dual-curing adhesive for bonding the engineering plastic body, wherein the dual-curing adhesive comprises a prepolymer resin, a diluent, a low dielectric modifier, an initiator, a catalyst, a dehydrating agent and a polymerization inhibitor; the prepolymer resin is obtained by reacting isocyanate containing vinyl and organopolysiloxane with amino or at least one hydrolyzable group at two molecular ends, the diluent comprises nitrogen-containing acrylate monomer, the low dielectric modifier is cage polysilsesquioxane or derivative thereof, the catalyst is dibutyl tin dilaurate, and the dehydrating agent is methyltrimethoxysilane; the adhesive has excellent adhesion to materials which are difficult to adhere, such as LCP, PP, PET, PEI and the like, and has low dielectric constant.
Description
Technical Field
The invention relates to the technical field of special plastic preparation, in particular to a composite engineering plastic with a low dielectric constant and a preparation method thereof.
Background
With the development of light weight of materials, engineering plastics are gradually becoming substitutes for materials such as metal and glass, compared with the materials such as metal and glass, the cost required for the production of a plastic substrate and the treatment process of the plastic substrate is relatively low, and the materials are environment-friendly and recyclable, so that the engineering plastics are widely applied.
Common engineering plastics include LCP, PP, PET and PEI, and in practical application, the assembly and bonding of the plastics are often required, and the plastics are generally difficult to bond by a common adhesive because the surface energy of the plastics is reduced in the processing process. To improve the adhesion of these materials, the surface properties are only modified by surface treatments, such as plasma treatment, corona discharge, chemical oxidation and primer coating, but these treatments are expensive, time consuming and sometimes not feasible; on the other hand, with the rapid development of the electronic industry, there is an increasing demand for the performance of materials, in particular, for the dielectric constant and dielectric loss of materials, because the larger the dielectric loss is, the larger the loss of signals during transmission is, and thus the lower the dielectric constant required for an adhesive for material bonding is.
In applications involving these low surface energy materials, hot melt adhesives, cyanoacrylates with primer systems, two-part epoxy resins and two-part acrylate adhesives have been developed. However, these adhesives do not meet the high-speed line requirements. Primer treatment or pre-mix treatment of the two-component adhesive is also a negative factor in practical applications. UV curable resins are one-component and can cure in a few seconds, which makes them a good choice in high speed production lines; to compensate for the curing of UV shadows, adhesives with dual UV-moisture curing have been developed, but their dielectric constants are generally large and bond strength to low surface energy materials is also to be improved.
Disclosure of Invention
In view of the above problems, the present invention provides a low dielectric constant composite engineering plastic and a preparation method thereof, and in particular relates to a modified organic silicone adhesive which can be used for a difficult-to-adhere material and low dielectric constant UV moisture dual curing, can be used for various insulating engineering plastic materials with low surface energy and difficult adhesion, and has a low dielectric constant.
The aim of the invention is realized by adopting the following technical scheme:
the composite engineering plastic with low dielectric constant comprises an engineering plastic body and a dual-curing adhesive for bonding the engineering plastic body, wherein the dual-curing adhesive comprises a prepolymer resin, a diluent, a low dielectric modifier, a photoinitiator, a catalyst, a dehydrating agent and a polymerization inhibitor;
the prepolymer resin is obtained by reacting isocyanate containing vinyl and organopolysiloxane with amino or at least one hydrolyzable group at two molecular ends;
the diluent comprises a nitrogenous acrylate monomer;
the inventors have found that most compatible reactive diluents are not readily UV curable, and that polyfunctional heterocyclyl methacrylates are a few monomers compatible with silicones and readily UV curable, and that the diluents also preferably include isobornyl acrylate, hydroxypropyl acrylate, 2-2-ethoxyethoxyethyl acrylate, and dicyclopentenyl glycol ether methacrylate, and combinations thereof, for compatibility with silicones and ease of curing;
the low dielectric modifier is one or more of cage polysilsesquioxane and derivatives thereof;
the cage-shaped framework structure of the cage-shaped Polysilsesquioxane (POSS) ensures that the adhesive has good dielectric property and optical property, in the toughening aspect, POSS nano particles can stop the development of micro crack tips and can trigger silver lines or shear bands or molecular chain rearrangement, the elasticity of the cage can play a role similar to that of a marble, and the introduction of the cage-shaped polysilsesquioxane can reduce the dielectric constant of the adhesive and increase the toughness of the adhesive;
the catalyst is dibutyl tin dilaurate, and the dehydrating agent is methyltrimethoxysilane.
Preferably, the mass ratio of the prepolymer resin to the diluent, the low dielectric modifier, the photoinitiator, the catalyst, the dehydrating agent and the polymerization inhibitor is 100: (20-100): (1-10): (3-6): (0.5-14.8): (0.4-0.6): (0.05-0.2).
Preferably, the prepolymer is a polydimethylsiloxane oligomer with vinyl end groups, and the preparation method comprises the following steps:
under the conditions of reduced pressure and room temperature, carrying out condensation reaction on silanol-terminated polydimethylsiloxane and R1 substituted aminopropyl trimethoxy silane under the condition of bismuth octoate catalyst, adding 2-isocyanatoethyl methacrylate with certain stoichiometric amount after the reaction is finished, stirring and reacting under the protective atmosphere, and obtaining the polydimethylsiloxane oligomer with vinyl end groups after the reaction is finished;
wherein the molar ratio of the silanol-terminated polydimethylsiloxane to the aminopropyl trimethoxysilane is 1: (2-2.2); the molecular weight of the silanol-terminated polydimethylsiloxane is 30000-50000, and the viscosity is 1000-1500 CPS;
further preferably, the silanol-terminated polydimethylsiloxane has a molecular weight of 26000 and a viscosity of 1000cps;
the vinyl-terminated polydimethylsiloxane oligomer has methoxy hydrolyzable groups at the molecular terminals and can be moisture crosslinked after UV curing.
Preferably, the addition weight of the bismuth octoate is 0.01-0.05wt% of the sum of the mass of the silanol-terminated polydimethylsiloxane and the mass of the R1-substituted aminopropyl trimethoxysilane.
Preferably, the R1 substituent is a hydrogen atom, methyl, ethyl, propyl, butyl or phenyl.
Preferably, the nitrogen-containing acrylate monomer is an acrylate monomer having an nitrogen heterocyclic group, the nitrogen-containing acrylate monomer having one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an epoxy group having 2 to 20 carbon atoms, and a hydroxyl group, the nitrogen heterocyclic group having one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms; more preferred is ethylene urea ethoxy methacrylate.
Preferably, the low dielectric modifier comprises derivative modified cage polysilsesquioxane, and the preparation method comprises the following steps:
weighing 2,2' -bis (trifluoromethyl) diaminobiphenyl under the condition of ice water bath, dissolving in dichloromethane, adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, fully stirring and mixing, adding carboxyl modified cage polysilsesquioxane and 5-norbornene-2-carboxylic acid, stirring and reacting overnight at room temperature, separating filtrate after the reaction is finished, adding a mixed solvent of methanol and acetone into the filtrate, fully stirring until no sediment is generated, separating the sediment, washing with the mixed solvent and deionized water in sequence, and drying to obtain the product;
wherein the mass ratio of the 2,2' -bis (trifluoromethyl) diaminobiphenyl to the dicyclohexylcarbodiimide, the 4-dimethylaminopyridine, the carboxyl modified cage-type polysilsesquioxane and the 5-norbornene-2-carboxylic acid is 10: (12.5-12.8): (1-1.2): (15-18): (4.5-5.2).
Preferably, the dual-curing adhesive comprises hexafluorobisphenol A and potassium carbonate, wherein the mass ratio of the hexafluorobisphenol A to the potassium carbonate to the 2,2' -bis (trifluoromethyl) diaminobiphenyl is 1: (0.2-0.4): (1.8-1.9).
Preferably, the photoinitiator is one or more of 11732-hydroxy-2-methyl-1-phenylpropion, 1841-hydroxycyclohexylphenyl ketone, 9072-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, TPO 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, TPO-L2, 4, 6-trimethylbenzoyl phenylphosphonate ethyl ester, IHT-PI 9102-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 6592-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and MBF benzoyl methyl formate.
The invention also provides a preparation method of the composite engineering plastic, which comprises the following steps:
(1) Weighing the raw materials according to the ratio and mixing to prepare the dual-curing adhesive;
(2) Coating the dual-curing adhesive on the engineering plastic body to be bonded;
(3) And (3) completing curing under the conditions of ultraviolet light and moisture in sequence to prepare the composite engineering plastic.
The beneficial effects of the invention are as follows:
(1) The adhesive has excellent adhesion to materials which are difficult to adhere, such as LCP, PP, PET, PEI and the like, and does not need any surface pretreatment. The polydimethylsiloxane oligomer has a hydrolyzable group of methoxy group at the molecular end, and after the adhesive is cured by UV, the shadow part can be cured by a secondary curing mechanism of moisture, so that the problem that the shadow part of the traditional UV adhesive cannot be cured due to insufficient illumination is solved, the moisture curing is used as strength compensation, the final strength of an elastomer after UV curing is improved, and compared with the process of UV curing only, the tensile strength is improved by 38% -72% by secondary moisture curing.
(2) According to the invention, cage-type polysilsesquioxane is introduced as a modifier on the basis of the polydimethylsiloxane oligomer, so that the dielectric property of the adhesive film is reduced, and a proper amount of nitrogenous acrylate monomer is introduced as an enhancer, and meanwhile, the adhesive property is improved.
(3) The invention adopts dibutyl tin dilaurate as a moisture curing catalystThe agent promotes secondary moisture curing without affecting the bonding strength and improves the elasticity, so that the adhesive is 300mJ/cm at room temperature 2 Can be completely cured within the energy, overcomes the defect of high curing energy of the existing product, has the volume shrinkage rate of less than 0.3 percent after curing, and avoids the problem of splitting of the thin plastic film due to the overhigh shrinkage rate.
(4) The adhesive of the invention is easy to prepare and is suitable for being used as an elastomer adhesive between engineering plastic parts, can also be used as an adhesive of sealing agents and filling materials which are difficult to adhere, and can achieve the following properties: the UV moisture dual curing, the low-energy LED cold light source curing, the shrinkage rate of less than 0.3%, the adhesive force of high, the dielectric constant of less than 2, the adhesive strength of more than 5MPa, the adhesive film being soft and elastic, the hardness of low (Shore A15-20), the adhesive film being difficult to generate the phenomenon of shrinkage fault and high in reliability.
Detailed Description
The invention will be further described with reference to the following examples.
The embodiment of the invention relates to a low dielectric constant UV-moisture dual-curable adhesive, which is prepared by the following steps:
(1) Preparation of polydimethylsiloxane oligomers
1 mole of silanol-terminated polydimethylsiloxane (molecular weight 26000, viscosity 1000 CPS) was reacted with 2.2 moles of R1-substituted aminopropyl trimethoxysilane (R) 1 Representing hydrogen, methyl, ethyl, propyl, butyl or phenyl) under the catalysis of 0.05wt% of bismuth octoate for 10 hours, removing methanol byproducts, adding 2-isocyanatoethyl methacrylate with a certain stoichiometric amount, and stirring and reacting for 90 minutes under the condition of nitrogen filling to obtain the polydimethylsiloxane oligomer with vinyl end groups;
the chemical reaction equation is as follows:
(2) Preparation of adhesive
And adding the obtained oligomer into an acrylate monomer diluent, cage polysilsesquioxane POSS or a derivative thereof, a photoinitiator, a dibutyltin dilaurate (DBTDL) moisture curing catalyst, a methyltrimethoxysilane dehydrating agent and a free radical polymerization inhibitor (polymerization inhibitor), and stirring under a nitrogen atmosphere to prepare the adhesive with low dielectric constant and UV-moisture dual curing.
The high oxygen permeability of the siloxane oligomer results in strong oxygen inhibition to maintain the surface tack after uv curing, and the surface curability can be improved by increasing the initiator concentration and increasing the light intensity, or by adding some readily oxidizable compound such as a thiol or amine. It has been found that the addition of moisture curing catalysts such as dibutyltin dilaurate also improves surface curability. By adding an appropriate amount of dibutyltin dilaurate to the formulation, at 300mJ/cm 2 Under UV light curing, the surface becomes tack free, the light curing energy can be reduced, and a low energy LED cold light source can be used for curing.
Examples 1 to 7
Preparation of the prepolymer: adding 1.5 mol of silanol-terminated polydimethylsiloxane (molecular weight is 26000, viscosity is 1000 CPS) and 3.2 mol of ethyl-substituted aminopropyl trimethoxysilane and 0.03g of bismuth octoate into a three-neck flask for condensation reaction for 6 hours in vacuum, then adding stoichiometric amount of 2-isocyanatoethyl methacrylate, stirring for 90 minutes under the condition of filling nitrogen to obtain polydimethylsiloxane oligomer with vinyl end groups, adding the obtained oligomer into an acrylic acid ester monomer diluent, a POSS siloxane low dielectric modifier, a photoinitiator, a dibutyl tin dilaurate (DBTDL) moisture curing catalyst, a methyltrimethoxysilane dehydrating agent and a free radical polymerization inhibitor (polymerization inhibitor) to prepare the adhesive under the condition of stirring under nitrogen;
the acrylate monomer diluent comprises ethylene urea ethoxy methacrylate, N.N Dimethylacrylamide (DMAA) or isobornyl acrylate (IBXA);
the POSS siloxane low dielectric modifier is cage Polysilsesquioxane (POSS) or derivative modified cage polysilsesquioxane (DPOSS), and the preparation method of the derivative modified cage polysilsesquioxane comprises the following steps:
under the ice water bath condition, weighing 10 parts of 2,2' -bis (trifluoromethyl) diaminobiphenyl according to parts by weight, dissolving in methylene dichloride, adding 12.6 parts of dicyclohexylcarbodiimide and 1.1 parts of 4-dimethylaminopyridine, fully stirring and mixing, adding 17 parts of carboxyl modified cage-type polysilsesquioxane and 4.8 parts of 5-norbornene-2-carboxylic acid, stirring and reacting overnight at room temperature, separating filtrate after the reaction is finished, adding a mixed solvent of methanol and acetone into the filtrate, fully stirring until no precipitate is generated, separating the precipitate, washing with the mixed solvent and deionized water in sequence, and drying to obtain the product;
the formulation components (parts by weight) and their associated indices for each example are shown in the following table:
the high-temperature high-humidity performance is the change rate of the optical performance after 1000 hours under the condition of 85% humidity at 85 ℃;
the excellent cold and hot impact performance is the change rate of optical performance after 1000 cycles of cold and hot impact at the temperature of-20 ℃ to 85 ℃.
The UV, moisture curable organosilicon compounds provided herein exhibit unexpectedly high adhesion strength to low surface energy materials, and the addition of IBXA monomers and nitrogen-containing monomers may play an important role in improving the surface adhesion between silicone gum and adherends, such as in photoinitiators that also have a low surface energy effect in improving adhesion.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The composite engineering plastic with low dielectric constant is characterized by comprising an engineering plastic body and a dual-curing adhesive for bonding the engineering plastic body, wherein the dual-curing adhesive comprises a prepolymer resin, a diluent, a low dielectric modifier, a photoinitiator, a catalyst, a dehydrating agent and a polymerization inhibitor;
the prepolymer resin is obtained by reacting isocyanate containing vinyl and organopolysiloxane with amino or at least one hydrolyzable group at two molecular ends;
the diluent comprises a nitrogenous acrylate monomer;
the low dielectric modifier is one or more of cage polysilsesquioxane and derivatives thereof;
the catalyst is dibutyl tin dilaurate, and the dehydrating agent is methyltrimethoxysilane.
2. The low dielectric constant composite engineering plastic according to claim 1, wherein the mass ratio of the prepolymer resin to the diluent, the low dielectric modifier, the photoinitiator, the catalyst, the dehydrating agent and the polymerization inhibitor is 100: (20-100): (1-10): (3-6): (0.5-14.8): (0.4-0.6): (0.05-0.2).
3. The low dielectric constant composite engineering plastic according to claim 1, wherein the prepolymer is a polydimethylsiloxane oligomer having vinyl end groups, and the preparation method comprises the following steps:
under the conditions of reduced pressure and room temperature, carrying out condensation reaction on silanol-terminated polydimethylsiloxane and R1 substituted aminopropyl trimethoxy silane under the condition of bismuth octoate catalyst, adding 2-isocyanatoethyl methacrylate with certain stoichiometric amount after the reaction is finished, stirring and reacting under the protective atmosphere, and obtaining the polydimethylsiloxane oligomer with vinyl end groups after the reaction is finished;
wherein the molar ratio of the silanol-terminated polydimethylsiloxane to the aminopropyl trimethoxysilane is 1: (2-2.2); the silanol-terminated polydimethylsiloxane has a molecular weight of 30000-50000 and a viscosity of 1000-1500 CPS.
4. A low dielectric constant composite engineering plastic according to claim 3, wherein the bismuth octoate is added in an amount of 0.01 to 0.05wt% based on the sum of the mass of the silanol-terminated polydimethylsiloxane and the mass of the R1-substituted aminopropyl trimethoxysilane.
5. The low dielectric constant composite engineering plastic according to claim 3 or 4, wherein the R1 substituent is a hydrogen atom, methyl, ethyl, propyl, butyl or phenyl.
6. The low dielectric constant composite engineering plastic according to claim 1, wherein the nitrogen-containing acrylate monomer is an acrylate monomer having an nitrogen heterocyclic group, the nitrogen-containing acrylate monomer has one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an epoxy group having 2 to 20 carbon atoms, and a hydroxyl group, and the nitrogen heterocyclic group has one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms.
7. The low dielectric constant composite engineering plastic according to claim 1, wherein the low dielectric modifier comprises derivative modified cage polysilsesquioxane, and the preparation method comprises the following steps:
weighing 2,2' -bis (trifluoromethyl) diaminobiphenyl under the condition of ice water bath, dissolving in dichloromethane, adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, fully stirring and mixing, adding carboxyl modified cage polysilsesquioxane and 5-norbornene-2-carboxylic acid, stirring and reacting overnight at room temperature, separating filtrate after the reaction is finished, adding a mixed solvent of methanol and acetone into the filtrate, fully stirring until no sediment is generated, separating the sediment, washing with the mixed solvent and deionized water in sequence, and drying to obtain the product;
wherein the mass ratio of the 2,2' -bis (trifluoromethyl) diaminobiphenyl to the dicyclohexylcarbodiimide, the 4-dimethylaminopyridine, the carboxyl modified cage-type polysilsesquioxane and the 5-norbornene-2-carboxylic acid is 10: (12.5-12.8): (1-1.2): (15-18): (4.5-5.2).
8. The low dielectric constant composite engineering plastic according to claim 7, wherein the dual curing adhesive comprises hexafluorobisphenol a and potassium carbonate, and the mass ratio of the hexafluorobisphenol a and the potassium carbonate to the 2,2' -bis (trifluoromethyl) diaminobiphenyl is 1: (0.2-0.4): (1.8-1.9).
9. The low dielectric constant composite engineering plastic according to claim 1, wherein the photoinitiator is one or more of hydroxy-2-methyl-1-phenylpropion, hydroxycyclohexylphenyl ketone, methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and methyl benzoate.
10. The method for preparing the composite engineering plastic according to any one of claims 1 to 9, comprising the following steps:
(1) Weighing the raw materials according to the ratio and mixing to prepare the dual-curing adhesive;
(2) Coating the dual-curing adhesive on the engineering plastic body to be bonded;
(3) And (3) completing curing under the conditions of ultraviolet light and moisture in sequence to prepare the composite engineering plastic.
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