CN106866719B - Benzocyclobutene polycarbosilane polymerization monomer or resin and preparation method thereof - Google Patents
Benzocyclobutene polycarbosilane polymerization monomer or resin and preparation method thereof Download PDFInfo
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- CN106866719B CN106866719B CN201710030375.6A CN201710030375A CN106866719B CN 106866719 B CN106866719 B CN 106866719B CN 201710030375 A CN201710030375 A CN 201710030375A CN 106866719 B CN106866719 B CN 106866719B
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- disilylocyclobutane
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- 239000000178 monomer Substances 0.000 title claims abstract description 43
- 229920003257 polycarbosilane Polymers 0.000 title claims abstract description 43
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920005989 resin Polymers 0.000 title claims abstract description 22
- 239000011347 resin Substances 0.000 title claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 93
- -1 3-dibenzocyclobutenyl Chemical group 0.000 claims abstract description 57
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 41
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 18
- YTEBBRBEZXVKCP-UHFFFAOYSA-N chloro-(chloromethyl)-methyl-propan-2-yloxysilane Chemical compound CC(C)O[Si](C)(Cl)CCl YTEBBRBEZXVKCP-UHFFFAOYSA-N 0.000 claims abstract description 17
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- GMHHTGYHERDNLO-UHFFFAOYSA-N 4-bromobicyclo[4.2.0]octa-1(6),2,4-triene Chemical compound BrC1=CC=C2CCC2=C1 GMHHTGYHERDNLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- JAYBZWYBCUJLNQ-UHFFFAOYSA-N dichloro-(chloromethyl)-methylsilane Chemical compound C[Si](Cl)(Cl)CCl JAYBZWYBCUJLNQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 118
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 90
- 239000007788 liquid Substances 0.000 claims description 90
- CBZNDCXNWNCBHK-UHFFFAOYSA-N methylidenesilane Chemical compound [SiH2]=C CBZNDCXNWNCBHK-UHFFFAOYSA-N 0.000 claims description 59
- 239000007787 solid Substances 0.000 claims description 57
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 53
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 50
- 239000002253 acid Substances 0.000 claims description 44
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 40
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 39
- 239000011777 magnesium Substances 0.000 claims description 38
- 229910052749 magnesium Inorganic materials 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 26
- 239000003208 petroleum Substances 0.000 claims description 25
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 22
- 239000011630 iodine Substances 0.000 claims description 22
- 229910052740 iodine Inorganic materials 0.000 claims description 22
- 238000007865 diluting Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000005457 ice water Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 239000003480 eluent Substances 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000010898 silica gel chromatography Methods 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- NTQGILPNLZZOJH-UHFFFAOYSA-N disilicon Chemical compound [Si]#[Si] NTQGILPNLZZOJH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- BBEWCCLSXIJGRR-UHFFFAOYSA-N 1,3-dimethyl-1,3-di(propan-2-yloxy)-1,3-disiletane Chemical compound CC(C)O[Si]1(C)C[Si](C)(OC(C)C)C1 BBEWCCLSXIJGRR-UHFFFAOYSA-N 0.000 claims description 7
- FMUGCKJYZCSVJC-UHFFFAOYSA-N chloromethyl-methyl-propan-2-yloxysilane Chemical compound C(C)(C)O[SiH](C)CCl FMUGCKJYZCSVJC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002329 infrared spectrum Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 36
- 229920001519 homopolymer Polymers 0.000 abstract description 9
- 238000004377 microelectronic Methods 0.000 abstract description 6
- 229920005684 linear copolymer Polymers 0.000 abstract description 5
- 230000007123 defense Effects 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 37
- 235000019441 ethanol Nutrition 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000011049 filling Methods 0.000 description 16
- 239000012535 impurity Substances 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 230000005526 G1 to G0 transition Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010791 quenching Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- NDKBSLOMSLZZBG-UHFFFAOYSA-N C1CC=2C1=CC=CC2.BrC2=CC=CC=C2 Chemical compound C1CC=2C1=CC=CC2.BrC2=CC=CC=C2 NDKBSLOMSLZZBG-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
- C07F7/0807—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane shown in formula (I) and a preparation method thereof, which is characterized in that: the preparation method of the benzocyclobutene polycarbosilane polymerization monomer comprises the following steps: under the protection of nitrogen, dropwise adding isopropanol into chloromethyl methyl dichlorosilane for reaction, and then carrying out reduced pressure distillation to obtain chloromethyl methyl isopropyloxy chlorosilane; preparing 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilicon cyclobutane; then the reaction product is stirred with a Grignard reagent of 4-bromobenzocyclobutene and the like for reaction, and then the product is obtained by separation and purification; further, polycarbosilane homopolymers and polycarbosilane linear copolymers can be prepared. The benzocyclobutene polycarbosilane resin prepared by the method has good thermal stability, chemical stability, mechanical property and electrical property, and is suitable for the fields of microelectronic industry, aerospace, national defense and the like.
Description
Technical Field
The invention belongs to a macromolecular compound obtained by reactions other than carbon-carbon unsaturated bonds, and relates to a benzocyclobutene polycarbosilane polymerization monomer or resin and a preparation method thereof. The benzocyclobutene polycarbosilane resin prepared by the method has good thermal stability, chemical stability, mechanical property and electrical property, and is suitable for the fields of microelectronic industry, aerospace, national defense and the like.
Background
Benzocyclobutene (BCB for short) materials have been widely used in military and civil fields since they have excellent high and low temperature resistance, weather resistance, good air tightness, radiation resistance, especially excellent film-forming property and moisture resistance. Common organic silicon high molecular polymers have excellent characteristics of high and low temperature resistance, weather resistance, electric insulation, irradiation resistance, flame retardance, good air tightness, corrosion resistance and the like, and are widely used in a plurality of important fields of aerospace and the like, but common organic silicon materials have poor film forming performance, and high molecular materials with good film forming performance can be prepared only by modifying specific functional groups. In the prior art, it has been reported (U.S. Pat. No. 5882836, 1999) to introduce BCB groups into silicone molecules, for example: tetramethyl divinyl siloxane bridged benzocyclobutene (DVSBCB) monomer, which can be polymerized to obtain organic silicon resin with excellent comprehensive performance, and is widely applied to the microelectronic device industry, such as the manufacture of semiconductor devices, the manufacture of electric insulating layers and substrates, the manufacture of MCM microelectronic devices, the packaging and bonding of waveguide devices and the like. However, the heat-resistant stability of the silicone resin material in the prior art needs to be further improved, the dielectric constant needs to be further reduced, and the preparation process steps need to be further simplified to meet different requirements.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a benzocyclobutene polycarbosilane polymerization monomer or resin and a preparation method thereof. The invention provides a benzocyclobutene polycarbosilane polymerization monomer and a novel organic silicon resin formed by homopolymerization and copolymerization of the monomer, the benzocyclobutene polycarbosilane polymerization monomer is prepared by Grignard reaction, a benzocyclobutene-containing linear polymer prepared by chloroplatinic acid catalysis ring opening is thermally cured, and the linear polymer is crosslinked into a resin with a network structure, so that the benzocyclobutene polycarbosilane polymerization monomer has extremely excellent thermal property (thermal decomposition temperature T)d>400 ℃ zero weight loss temperature T0>350 ℃), mechanical properties (the film hardness is adjustable and is measured by a pencil scratch method from 4H to 8H), electrical properties (the dielectric constant is 2.3 to 2.7) and film forming properties (the maximum height difference of the film is 3nm to 10nm, and the film is measured by an atomic force microscope), is suitable for large-scale batch production, and has wide application prospect as a high-performance dielectric film material or a packaging material in the fields of microelectronic industry, aerospace, national defense and the like.
The content of the invention comprises: polymerized monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane (DMDBDSCB for short) and a preparation method thereof; polymethyl benzocyclobutene methylene silane (PMBSM for short) and a method for preparing polycarbosilane homopolymer through ring-opening polymerization of 1, 3-dimethyl-1, 3-dibenzocyclobutenyldisilacyclobutane (DMDBDSCB for short) catalyzed by chloroplatinic acid; and a method for preparing a polycarbosilane linear copolymer, namely polymethylphenylmethylenesilane/polymethylbenzocyclobutenylmethylenesilane (PMPSM-co-PMBSM for short), by ring-opening polymerization of polymethylphenylmethylenesilane/polymethylbenzocyclobutenyldisilacyclobutane (DMDBDSCB for short) and 1, 3-dimethyl-1, 3-diphenyldisilicon-cyclobutane (DMDPB for short) under the catalysis of chloroplatinic acid.
The content of the invention is as follows: 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilicon cyclobutane, which is characterized in that the benzocyclobutene polycarbosilane polymer monomer has a chemical structural formula shown in a formula (I):
another aspect of the invention is: the preparation method of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane is characterized by comprising the following steps:
a. synthesis of chloromethyl methyl isopropyloxysilane:
in an ice-water bath, 22.89g of chloromethyl methyl dichlorosilane is added into a reactor under the protection of nitrogen; adding 7.8g of isopropanol into a constant-pressure dropping funnel, and slowly dropping the isopropanol into the reactor for 2-4 h; after the dropwise addition is finished, continuously reacting for 1-2 h at room temperature; introducing nitrogen gas directly in the whole reaction process to take away hydrogen chloride gas generated in the reaction process; after the reaction is finished, carrying out reduced pressure distillation on the solution after the reaction, and collecting fractions under the conditions that the temperature is 55-60 ℃ and the pressure is 0.4-0.5 Torr to obtain colorless transparent liquid, namely the prepared chloromethyl methyl isopropyloxy chlorosilane;
b. synthesis of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilacyclobutane:
adding 1.64-2.78 g of magnesium and 0.011-0.013 g of iodine into a reactor; adding 5-10 mL of tetrahydrofuran and 0.1-0.3 mL of dibromoethane into a reactor under the protection of nitrogen; taking 10g of chloromethyl methyl isopropyloxy chlorosilane prepared in the step a, and diluting the chloromethyl methyl isopropyloxy chlorosilane in 26mL of tetrahydrofuran to obtain a mixed solution; dropwise adding a few drops of mixed liquid under the protection of nitrogen at room temperature to contact magnesium (strips) and iodine for a slight heat initiation reaction, then moving the system into an ice-water bath, continuously (slowly) dropwise adding the mixed liquid for 1-2 hours, after the addition, moving the system into the room temperature, stirring for reaction for 2-3 hours (the optimal reaction time is 2 hours, and then continuously reacting for 2-3 hours at 50-60 ℃ (the optimal reaction time is 2 hours), after the reaction is finished, carrying out reduced pressure distillation on the reacted solution, and collecting fractions at the temperature of 50-55 ℃ and the pressure of 0.4-0.5 Torr to obtain colorless transparent liquid, namely the prepared 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylobutane;
c. synthesis of polymerized monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane:
adding 0.011-0.013 g of iodine and 1.64-2.78 g of magnesium into a reactor, vacuumizing and filling nitrogen; weighing 10.58g of 4-bromobenzocyclobutene, diluting the mixture in 27mL tetrahydrofuran (THF for short) to obtain a mixed solution, dropwise adding a few drops of the mixed solution at room temperature under the protection of nitrogen, contacting magnesium strips and iodine, slightly heating to initiate reaction, continuously (slowly) dropwise adding the mixed solution under the condition of ice-water bath, stirring for reaction, and finishing the addition within 1-2 hours; after the addition is finished, moving the system to room temperature, and stirring for reaction for 2-3 h to obtain a Grignard reagent of 4-bromobenzocyclobutene; adding 6.73g of the 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane prepared in the step b, and stirring and reacting at the temperature of 40-60 ℃ for 3-5 hours to obtain white slurry;
separation and purification: after the reaction is finished, cooling the obtained white slurry to room temperature, adding 3M (namely 3mol/L) of dilute hydrochloric acid (the amount of the added dilute hydrochloric acid is enough to react the rest magnesium sheets in the reaction) to quench the redundant Grignard reagent, extracting with 20mL of petroleum ether (preferably petroleum ether with the boiling range of 60-90 ℃) for 3 times, combining organic phases, washing with dilute hydrochloric acid, sodium bicarbonate aqueous solution and water in sequence, adding anhydrous sodium sulfate to dry for 3-4 h, concentrating by (rotary) evaporation (instrument) to remove most of the solvent to obtain light yellow liquid, performing silica gel column chromatography to obtain (silica gel column chromatography (300-400 meshes) and petroleum ether as a developing agent, concentrating by a rotary evaporator to remove the solvent ] to obtain benzocyclobutene polycarbosilane polymer monomer (I) -1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilicon cyclobutane (DMDBDSCB);
the benzocyclobutene polycarbosilane polymerization monomer (I) is characterized in that: colorless transparent crystals, the structure is characterized as follows:
1H NMR(600MHz,CDCl3)δ(ppm):7.70(d,1H,ArH),7.63(d,1H,ArH),7.56(d,1H,ArH),7.47(s,1H,ArH),7.29(d,1H,ArH),7.24(d,1H,ArH),3.41-3.36(d,8H,-CH2CH2-),0.53(s,6H,Si-CH3),0.42(s,4H,SiCH2Si).；
13C NMR(151MHz,CDCl3)δ(ppm):121-148(C6H5),29.94(s,-CH2CH2-),29.90(s,-CH2CH2-),29.83(s,-CH2CH2-),29.79(s,-CH2CH2-),2.37(s,SiCH2Si),2.32(s,SiCH2Si),1.69(s,Si-CH3),1.63(s,Si-CH3).。
another aspect of the invention is: the polymethylbenzocyclobutene methylene silane is characterized in that the benzocyclobutene polycarbosilane resin has a chemical structural formula shown in a formula (II):
the molecular weight of the polymethylbenzocyclobutene methylene silane (II) is 30000-40000.
Another aspect of the invention is: the preparation method of the polymethylbenzocyclobutene methylene silane is characterized by comprising the following steps:
a. preparing materials: taking 2.9mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane (DMDBDSCB for short) as a raw material; taking a catalyst chloroplatinic acid, diluting the chloroplatinic acid in tetrahydrofuran, and preparing tetrahydrofuran solution of the chloroplatinic acid with the concentration of 0.025M (namely 0.025mol/L)) for later use;
b. reaction: under the protection of nitrogen, injecting 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane and 50 mu L tetrahydrofuran solution of chloroplatinic acid into a reactor, and reacting at the temperature of 80-100 ℃ for 18-24 h to obtain reacted liquid;
c. separation and purification: subjecting the reacted liquid obtained in the step b to column chromatography (specifically, the method comprises the steps of sequentially filling 2g of diatom powder, 2g of diatomite and 1g of 100-mesh 200-mesh alumina as a stationary phase and toluene as an eluent into the column from bottom to top), distilling and concentrating the eluted liquid to remove (most) the eluent to obtain a colorless liquid, precipitating the colorless liquid in ethanol (specifically, the method comprises the steps of dropwise adding the colorless liquid into anhydrous ethanol with a volume four times that of the volume of the colorless liquid, precipitating the solid in the ethanol, filtering to obtain a solid, the method is the prior art, dissolving the solid in a proper amount of toluene, dropwise adding the dissolved solid into anhydrous ethanol with a volume four times that of the volume of the solid, precipitating the solid in the ethanol, filtering to obtain a solid, repeating the process for 3 times to remove impurities and low molecular weight polymers), drying the obtained solid (preferably, drying in a vacuum drying box at 50 ℃ for 12-20 hours), thus obtaining polycarbosilane linear homopolymer, namely poly (methyl benzocyclobutene methylene silane) (PMBSM for short) (II);
the linear polycarbosilane homopolymer (d) is characterized in that: white viscous oil, structure characterized as follows:
1H NMR(600MHz，CDCl3)δ(ppm):0.0-0.1(multi),3.1-3.4(multi),7.1-7.4(br,multi)；
13C NMR(151MHz,CDCl3)δ(ppm):-0.24,0.05,6.0,6.2,6.4,29.7,29.8，127.8,128.8,134.1,141.4.；
infrared Spectrum IR (KBr coated, cm)-1)：3066,2955,2899,2861,1588,1457，1250,1050,733,698。
Another aspect of the invention is: the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane is characterized in that the benzocyclobutene polycarbosilane resin has a chemical structural formula shown in a formula (III):
the molecular weight of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane (III) is 40000-300000.
Another aspect of the invention is: the preparation method of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane is characterized by comprising the following steps:
a. preparing materials: taking 0.6mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane (DMDBDSCB for short) as a raw material; 5.4mmol of 1, 3-dimethyl-1, 3-diphenyl disilylocyclobutane (DMDPDSB for short); taking a catalyst chloroplatinic acid, diluting the chloroplatinic acid in tetrahydrofuran, and preparing tetrahydrofuran solution of the chloroplatinic acid with the concentration of 0.025M (namely 0.025 mol/L); (monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyldisilacyclobutane: DMDPDSBCB: catalyst chloroplatinic acid in a molar ratio of 1:1: 8.6X 10 is preferred-4) And is ready for use;
b. reaction: under the protection of nitrogen, injecting 0.6mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilyloxane butane (DMDBDSCB for short), 5.4mmol of 1, 3-dimethyl-1, 3-diphenyl disilyloxane butane (DMDPDSB for short) and 100 mu L of tetrahydrofuran solution of chloroplatinic acid into a reactor, and reacting at the temperature of 80-100 ℃ for 18-24 h (the optimal reaction time is 24h) to obtain a reacted liquid;
c. separation and purification: subjecting the reacted liquid obtained in the step b to column chromatography (specifically, the method comprises the steps of sequentially filling 4g of diatom powder, 4g of diatomite and 2g of 100 alumina with-200 meshes as a stationary phase and toluene as an eluent into the column from bottom to top), distilling and concentrating the eluted liquid to remove the eluent to obtain a colorless liquid, precipitating the colorless liquid in ethanol (specifically, the method comprises the steps of dropwise adding the colorless liquid into absolute ethanol with a volume four times that of the colorless liquid, precipitating the solid in the ethanol, filtering to obtain a solid, the method is the prior art, dissolving the solid in a proper amount of toluene, dropwise adding the dissolved solid into absolute ethanol with a volume four times that of the colorless liquid, precipitating the solid in the ethanol, filtering to obtain a solid, repeating the process for 3 times to remove impurities and low molecular weight polymers), drying the obtained solid (preferably, drying in a vacuum drying oven at 50 ℃ for 12-20 hours), thus preparing polycarbosilane linear copolymer-polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane (PMPSM-co-PMBSM for short) (III);
the basic characteristics of the polycarbosilane linear copolymer are as follows: a white viscous oil; the structure is characterized as follows:
1H NMR(600MHz,CDCl3)δ(ppm):0.0-0.2(multi),3.1-3.4(multi),7.1-7.6(br,multi).；
13C NMR(151MHz,CDCl3)δ(ppm):-0.27,0.07,6.0,6.2,6.5,29.8,29.9,127.4,128.6,134.2,141.3.；
infrared Spectrum IR (KBr coated, cm)-1)：3024,2955,2910,2849,1588,1456,1253,1050,735,698.。
In the preparation method of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane, the synthesis method of the polymerized monomer 1, 3-dimethyl-1, 3-diphenyl disilicon cyclobutane (DMDPDSB) is as follows:
a. preparing materials: taking 0.011-0.013 g of raw materials iodine, 1.64-2.78 g of magnesium, 9.076g (0.058mol) of bromobenzene, 6.73g (0.029mol) of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane (preferably prepared according to the molar ratio of bromobenzene: 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane being 2: 1), and tetrahydrofuran (THF for short) for later use;
b. reaction: adding iodine and magnesium into a reactor, diluting bromobenzene in 25mL tetrahydrofuran to obtain a mixed solution, dropwise adding a few drops of the mixed solution (the mixed solution is the mixed solution of bromobenzene and tetrahydrofuran) at room temperature under the protection of nitrogen gas, contacting a magnesium strip and iodine, slightly heating to initiate reaction, then continuously (slowly) dropwise adding the mixed solution in an ice water bath (about 0 ℃), and finishing the addition for 1-2 hours; after the addition is finished, stirring and reacting for 2-3 h at room temperature (the optimal reaction time is 2h) to obtain a gray solution, namely a bromobenzene Grignard reagent; adding 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane (prepared by synthesizing the 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane) and stirring to react for 3-5 hours at the temperature of 50-60 ℃ to obtain white slurry;
c. separation and purification: cooling the obtained white slurry to room temperature, adding 3M (namely 3mol/L) of dilute hydrochloric acid (the amount of the added dilute hydrochloric acid is enough to react the rest magnesium sheets in the reaction) to quench the redundant Grignard reagent, extracting with 20mL of petroleum ether (preferably petroleum ether with a boiling range of 60-90 ℃), extracting for 3 times, combining organic phases, washing with dilute hydrochloric acid, sodium bicarbonate aqueous solution and water in sequence, adding anhydrous sodium sulfate to dry for 3-4 h, concentrating and removing (most) solvent by (rotary) evaporation (instrument) to obtain light yellow liquid, and performing silica gel column chromatography to obtain a polymerized monomer 1, 3-dimethyl-1, 3-diphenyldisilicon cyclobutane (DMDPSCB) [ silica gel column chromatography (300-400 meshes), petroleum ether is a developing agent, and the solvent is removed by rotary evaporator concentration ];
the basic characteristics of the polymerized monomer 1, 3-dimethyl-1, 3-diphenyldisilylocyclobutane (DMDPDSBCB): a colorless transparent liquid; the structure is characterized as follows:
1H NMR(600MHz,CDCl3)δ(ppm):7.66-7.63(m,2H,ArH),7.56(d,2H,ArH),7.39(d,3H,ArH),7.34-7.31(m,3H,ArH),0.58(s,6H,Si-CH3),0.46(s,4H,SiCH2Si).；
13C NMR(151MHz,CDCl3)δ(ppm):127-142(C6H5),2.41(s,SiCH2Si),2.49(s,SiCH2Si),1.47(s,Si-CH3),1.50(s,Si-CH3).。
the synthesis of the polymerized monomer 1, 3-dimethyl-1, 3-diphenyldisilylocyclobutane (DMDPDSBCB) can also adopt the prior art.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) the benzocyclobutene polycarbosilane resin provided by the invention has excellent thermal stability, chemical stability, mechanical property and electrical property, and moderate curing temperature, and is suitable for large-scale batch production;
(2) the synthesized benzocyclobutene polycarbosilane resin is characterized in that linear homopolymer polymethylphenyl methylene silane (PMBSM for short) and copolymer polymethylphenyl methylene silane/polymethylbenzo are respectively synthesized by introducing monomers containing benzocyclobutene groups into carbosilane side chainsCyclobutenyl methylene silane (PMPSM-co-PMBSM for short), the linear polymer structure contains rigid aromatic ring side group, increases the free volume between molecules, thereby reduces the dielectric constant and loss of resin; and the benzocyclobutene functional group on its side chain has very high reactivity, can open the ring under high temperature, with the resin of linear polymer cross-linking network structure, after the complete crosslinking of benzocyclobutene functional group, not only improved the glass transition temperature of resin greatly, improved the thermal weightlessness temperature of resin moreover, the concrete expression is: extremely excellent thermal properties (thermal decomposition temperature T)d>400 ℃ zero weight loss temperature T0>350 ℃), electrical properties (dielectric constant is 2.3-2.7), excellent mechanical properties (the hardness of the film is adjustable and ranges from 4H to 8H) and film-forming properties (the maximum height difference of the film is 3 nm-10 nm);
(3) the preparation method has the advantages of simple preparation process, simple and convenient process, easy operation and strong practicability; the prepared polycarbosilane type benzocyclobutene resin has excellent performance, is suitable for the fields of microelectronic industry, aerospace, national defense and the like, and belongs to the technical field of new generation electronics, such as: the BCB waveguide device has wide application prospects in the aspects of packaging, surface texture treatment of the light-emitting diode, manufacturing of a dielectric interlayer connected inside a flip chip (flip to chip), manufacturing of high-power short-pulse Vertical Cavity Surface Emitting Laser (VCSELs) substrates and the like.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Example 1:
1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilicon cyclobutane, the benzocyclobutene polycarbosilane polymerized monomer has a chemical structural formula shown in formula (I):
example 2:
the preparation method of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane comprises the following steps:
a. synthesis of chloromethyl methyl isopropyloxysilane:
in an ice-water bath, 22.89g of chloromethyl methyl dichlorosilane is added into a reactor under the protection of nitrogen; adding 7.8g of isopropanol into a constant-pressure dropping funnel, and slowly dropping the isopropanol into the reactor for 2 hours; after the dropwise addition is finished, continuously reacting for 1h at room temperature; introducing nitrogen gas directly in the whole reaction process to take away hydrogen chloride gas generated in the reaction process; after the reaction is finished, carrying out reduced pressure distillation on the solution after the reaction, and collecting fractions under the conditions that the temperature is 55-60 ℃ and the pressure is 0.4-0.5 Torr to obtain colorless transparent liquid, namely the prepared chloromethyl methyl isopropyloxy chlorosilane;
b. synthesis of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilacyclobutane:
adding 1.64g of magnesium and 0.011g of iodine into a reactor, vacuumizing and filling nitrogen; adding 5mL of tetrahydrofuran and 0.1mL of dibromoethane into the reactor under the protection of nitrogen; taking 10g of chloromethyl methyl isopropyloxy chlorosilane prepared in the step a, and diluting the chloromethyl methyl isopropyloxy chlorosilane in 26mL of tetrahydrofuran to obtain a mixed solution; dropwise adding a few drops of mixed liquid under the protection of nitrogen at room temperature to contact magnesium (strips) and iodine for a slight heat to initiate reaction, then moving the system into an ice-water bath, continuously (slowly) dropwise adding the mixed liquid for 1 hour, moving the system into the room temperature after the addition is finished, stirring for reaction for 3 hours (the optimal reaction time is 2 hours, and then continuously reacting for 3 hours at 50 ℃), carrying out reduced pressure distillation on the reacted solution after the reaction is finished, and collecting fractions at the temperature of 50-55 ℃ and the pressure of 0.4-0.5 Torr to obtain colorless transparent liquid, namely the prepared 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilicon cyclobutane;
c. synthesis of polymerized monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane:
adding 0.011g of iodine and 1.64g of magnesium into a reactor, vacuumizing and filling nitrogen; weighing 10.58g of 4-bromobenzocyclobutene, diluting the mixture in 27mL tetrahydrofuran to obtain a mixed solution, dropwise adding a few drops of the mixed solution at room temperature under the protection of nitrogen, contacting magnesium strips and iodine, and slightly heating to initiate reaction, then continuously (slowly) dropwise adding the mixed solution under the condition of ice-water bath, stirring for reaction, and finishing the addition within 1 h; after the addition is finished, moving the system to room temperature, and stirring for reaction for 3 hours to obtain a Grignard reagent of 4-bromobenzocyclobutene; adding 6.73g of the 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane prepared in the step b, and stirring and reacting for 3 hours at the temperature of 40-60 ℃ to obtain white slurry;
separation and purification: after the reaction is finished, cooling the obtained white slurry to room temperature, adding 3M (namely 3mol/L) of dilute hydrochloric acid (the amount of the added dilute hydrochloric acid is enough to react the rest magnesium sheets in the reaction) to quench the redundant Grignard reagent, extracting with 20mL of petroleum ether (preferably petroleum ether with the boiling range of 60-90 ℃) for 3 times, combining organic phases, washing with dilute hydrochloric acid, sodium bicarbonate aqueous solution and water in sequence, adding anhydrous sodium sulfate for drying for 3 hours, concentrating by (rotary) evaporation (instrument) to remove most of the solvent to obtain light yellow liquid, performing silica gel column chromatography to obtain (silica gel column chromatography (300-400 meshes), wherein the petroleum ether is a developing agent, concentrating by a rotary evaporator to remove the solvent ] to obtain the benzocyclobutene polycarbosilane polymer monomer (I) -1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilicon cyclobutane (DMDBDSCB for short).
Example 3:
the preparation method of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane comprises the following steps:
a. synthesis of chloromethyl methyl isopropyloxysilane:
in an ice-water bath, 22.89g of chloromethyl methyl dichlorosilane is added into a reactor under the protection of nitrogen; adding 7.8g of isopropanol into a constant-pressure dropping funnel, and slowly dropping the isopropanol into the reactor for 4 hours; after the dropwise addition is finished, continuously reacting for 1h at room temperature; introducing nitrogen gas directly in the whole reaction process to take away hydrogen chloride gas generated in the reaction process; after the reaction is finished, carrying out reduced pressure distillation on the solution after the reaction, and collecting fractions under the conditions that the temperature is 55-60 ℃ and the pressure is 0.4-0.5 Torr to obtain colorless transparent liquid, namely the prepared chloromethyl methyl isopropyloxy chlorosilane;
b. synthesis of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilacyclobutane:
adding 2.78g of magnesium and 0.013g of iodine into a reactor, vacuumizing and filling nitrogen; adding 10mL of tetrahydrofuran and 0.3mL of dibromoethane into the reactor under the protection of nitrogen; taking 10g of chloromethyl methyl isopropyloxy chlorosilane prepared in the step a, and diluting the chloromethyl methyl isopropyloxy chlorosilane in 26mL of tetrahydrofuran to obtain a mixed solution; dropwise adding a few drops of mixed liquid under the protection of nitrogen at room temperature to contact magnesium (strips) and iodine for a slight heat to initiate reaction, then moving the system into an ice-water bath, continuously (slowly) dropwise adding the mixed liquid for 2 hours, moving the system into the room temperature after the addition is finished, stirring for reaction for 2 hours (the optimal reaction time is 2 hours, and then continuously reacting for 2 hours at 60 ℃), carrying out reduced pressure distillation on the reacted solution after the reaction is finished, and collecting fractions at the temperature of 50-55 ℃ and the pressure of 0.4-0.5 Torr to obtain colorless transparent liquid, namely the prepared 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilicon cyclobutane;
c. synthesis of polymerized monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane:
adding 0.013g of iodine and 2.78g of magnesium into a reactor, vacuumizing and filling nitrogen; weighing 10.58g of 4-bromobenzocyclobutene, diluting the mixture in 27mL tetrahydrofuran to obtain a mixed solution, dropwise adding a few drops of the mixed solution at room temperature under the protection of nitrogen, contacting magnesium strips and iodine, and slightly heating to initiate reaction, then continuously (slowly) dropwise adding the mixed solution under the condition of ice-water bath, stirring for reaction, and finishing the addition within 2 hours; after the addition is finished, moving the system to room temperature, and stirring for reaction for 2 hours to obtain a Grignard reagent of 4-bromobenzocyclobutene; then adding 6.73g of the 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane prepared in the step b, and stirring and reacting for 3 hours at the temperature of 60 ℃ to obtain white slurry;
separation and purification: after the reaction is finished, cooling the obtained white slurry to room temperature, adding 3M (namely 3mol/L) of dilute hydrochloric acid (the amount of the added dilute hydrochloric acid is enough to react the rest magnesium sheets in the reaction) to quench the redundant Grignard reagent, extracting with 20mL of petroleum ether (preferably petroleum ether with the boiling range of 60-90 ℃) for 3 times, combining organic phases, washing with dilute hydrochloric acid, sodium bicarbonate aqueous solution and water in sequence, adding anhydrous sodium sulfate for drying for 4 hours, concentrating by (rotary) evaporation (instrument) to remove most of the solvent to obtain light yellow liquid, performing silica gel column chromatography to obtain (silica gel column chromatography (300-400 meshes), wherein the petroleum ether is a developing agent, concentrating by a rotary evaporator to remove the solvent ] to obtain the benzocyclobutene polycarbosilane polymer monomer (I) -1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilicon cyclobutane (DMDBDSCB for short).
Example 4:
the benzocyclobutene polycarbosilane resin has a chemical structural formula shown in a formula (II):
the molecular weight of the polymethylbenzocyclobutene methylene silane (II) is 30000-40000.
Example 5:
the preparation method of the polymethylbenzocyclobutene methylene silane comprises the following steps:
a. preparing materials: taking 2.9mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane (DMDBDSCB for short) as a raw material; taking a catalyst chloroplatinic acid, diluting the chloroplatinic acid in tetrahydrofuran, and preparing tetrahydrofuran solution of the chloroplatinic acid with the concentration of 0.025M (namely 0.025mol/L)) for later use;
b. reaction: under the protection of nitrogen, 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane and 50 mu L tetrahydrofuran solution of chloroplatinic acid are injected into a reactor and react for 24 hours at the temperature of 80 ℃ to obtain liquid after reaction; c. separation and purification: subjecting the reacted liquid obtained in step b to column chromatography (specifically, the method comprises sequentially loading 2g of diatom powder, 2g of diatomite and 1g of 100-mesh 200-mesh alumina as a stationary phase and toluene as an eluent into the column from bottom to top), distilling and concentrating the eluted liquid to remove (most) the eluent to obtain a colorless liquid, precipitating the colorless liquid in ethanol (specifically, the method comprises the steps of dropwise adding the colorless liquid into four times of volume of absolute ethanol, precipitating the solid in ethanol, filtering to obtain a solid, the method is the prior art, dissolving the solid in a proper amount of toluene, dropwise adding the dissolved solid into four times of volume of absolute ethanol, precipitating the solid in ethanol, filtering to obtain a solid, repeating the process for 3 times to remove impurities and low molecular weight polymers), drying the obtained solid (preferably, drying in a vacuum drying oven at 50 ℃ for 12 hours), thus obtaining the polycarbosilane linear homopolymer, namely the polymethylbenzocyclobutene methylene silane (PMBSM for short) (II).
Example 6:
the preparation method of the polymethylbenzocyclobutene methylene silane comprises the following steps:
a. preparing materials: taking 2.9mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane (DMDBDSCB for short) as a raw material; taking a catalyst chloroplatinic acid, diluting the chloroplatinic acid in tetrahydrofuran, and preparing tetrahydrofuran solution of the chloroplatinic acid with the concentration of 0.025M (namely 0.025mol/L)) for later use;
b. reaction: under the protection of nitrogen, 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane and 50 mu L tetrahydrofuran solution of chloroplatinic acid are injected into a reactor and react for 18h at the temperature of 100 ℃ to obtain reacted liquid;
c. separation and purification: subjecting the reacted liquid obtained in step b to column chromatography (specifically, the method comprises sequentially loading 2g of diatom powder, 2g of diatomite and 1g of 100-mesh 200-mesh alumina as a stationary phase and toluene as an eluent into the column from bottom to top), distilling and concentrating the eluted liquid to remove (most) the eluent to obtain a colorless liquid, precipitating the colorless liquid in ethanol (specifically, the method comprises the steps of dropwise adding the colorless liquid into four times of volume of absolute ethanol, precipitating the solid in ethanol, filtering to obtain a solid, the method is the prior art, dissolving the solid in a proper amount of toluene, dropwise adding the dissolved solid into four times of volume of absolute ethanol, precipitating the solid in ethanol, filtering to obtain a solid, repeating the process for 3 times to remove impurities and low molecular weight polymers), drying the obtained solid (preferably, drying in a vacuum drying oven at 50 ℃ for 20 hours), thus obtaining the polycarbosilane linear homopolymer, namely the polymethylbenzocyclobutene methylene silane (PMBSM for short) (II).
Example 7:
polymethylphenylmethylene silane/polymethylbenzocyclobutenylmethylene silane, the benzocyclobutene polycarbosilane resin having the chemical structural formula shown in formula (III):
the molecular weight of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane (III) is 40000-300000.
Example 8:
the preparation method of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane comprises the following steps:
a. preparing materials: taking 0.6mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane (DMDBDSCB for short) as a raw material; 5.4mmol of 1, 3-dimethyl-1, 3-diphenyl disilylocyclobutane (DMDPDSB for short); taking a catalyst chloroplatinic acid, diluting the chloroplatinic acid in tetrahydrofuran, and preparing tetrahydrofuran solution of the chloroplatinic acid with the concentration of 0.025M (namely 0.025 mol/L); (monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyldisilacyclobutane: DMDPDSBCB: catalyst chloroplatinic acid in a molar ratio of 1:1: 8.6X 10 is preferred-4) And is ready for use;
b. reaction: under the protection of nitrogen, injecting 0.6mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilyloxane butane (DMDBDSCB for short), 5.4mmol of 1, 3-dimethyl-1, 3-diphenyl disilyloxane butane (DMDPDSB for short) and 100 mu L of tetrahydrofuran solution of chloroplatinic acid into a reactor, and reacting at the temperature of 80 ℃ for 24 hours (the optimal reaction time is 24 hours) to obtain a liquid after reaction;
c. separation and purification: subjecting the reacted liquid obtained in step b to column chromatography (specifically, from bottom to top, 4g of diatom powder, 4g of diatomite and 2g of 100 alumina with-200 meshes as a stationary phase and toluene as an eluent) are sequentially filled into the column, the eluent is removed through distillation and concentration of the eluted liquid to obtain a colorless liquid, the colorless liquid is precipitated in ethanol (specifically, the colorless liquid is dripped into absolute ethanol with a volume four times that of the colorless liquid, the solid is precipitated in ethanol, and the solid is filtered to obtain a solid, the method is the prior art, the solid can be dissolved in a proper amount of toluene and dripped into absolute ethanol with a volume four times that of the colorless liquid, the solid is precipitated in ethanol and filtered to obtain a solid, the process can be repeated for 3 times to remove impurities and low molecular weight polymers), the obtained solid is dried (preferably, the obtained solid is dried in a vacuum drying oven at 50 ℃ for 12 hours), thus obtaining the polycarbosilane linear copolymer-polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane (PMPSM-co-PMBSM for short) (III).
Example 9:
the preparation method of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane comprises the following steps:
a. preparing materials: taking 0.6mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane (DMDBDSCB for short) as a raw material; 5.4mmol of 1, 3-dimethyl-1, 3-diphenyl disilylocyclobutane (DMDPDSB for short); taking a catalyst chloroplatinic acid, diluting the chloroplatinic acid in tetrahydrofuran, and preparing tetrahydrofuran solution of the chloroplatinic acid with the concentration of 0.025M (namely 0.025 mol/L); (monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyldisilacyclobutane: DMDPDSBCB: catalyst chloroplatinic acid in a molar ratio of 1:1: 8.6X 10 is preferred-4) And is ready for use;
b. reaction: under the protection of nitrogen, injecting 0.6mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilyloxane butane (DMDBDSCB for short), 5.4mmol of 1, 3-dimethyl-1, 3-diphenyl disilyloxane butane (DMDPDSB for short) and 100 mu L of tetrahydrofuran solution of chloroplatinic acid into a reactor, and reacting at 100 ℃ for 18h (the optimal reaction time is 24h) to obtain a liquid after reaction;
c. separation and purification: subjecting the reacted liquid obtained in step b to column chromatography (specifically, from bottom to top, 4g of diatom powder, 4g of diatomite and 2g of 100 alumina with-200 meshes as a stationary phase and toluene as an eluent) are sequentially filled into the column, the eluent is removed through distillation and concentration of the eluted liquid to obtain a colorless liquid, the colorless liquid is precipitated in ethanol (specifically, the colorless liquid is dripped into absolute ethanol with a volume four times that of the colorless liquid, the solid is precipitated in ethanol, and the solid is filtered to obtain a solid, the method is the prior art, the solid can be dissolved in a proper amount of toluene and dripped into absolute ethanol with a volume four times that of the colorless liquid, the solid is precipitated in ethanol and filtered to obtain a solid, the process can be repeated for 3 times to remove impurities and low molecular weight polymers), the obtained solid is dried (preferably, the obtained solid is dried in a vacuum drying oven at 50 ℃ for 20 hours), thus obtaining the polycarbosilane linear copolymer-polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane (PMPSM-co-PMBSM for short) (III).
Example 10:
the preparation method of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane comprises the following steps of:
a. preparing materials: taking 0.011g of iodine, 2.78g of magnesium, 9.076g (0.058mol) of bromobenzene, 6.73g (0.029mol) of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane (preferably prepared according to the molar ratio of bromobenzene: 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane of 2: 1) and tetrahydrofuran (THF for short) for later use;
b. reaction: adding iodine and magnesium into a reactor, vacuumizing and filling nitrogen; diluting bromobenzene in 25mL tetrahydrofuran to obtain a mixed solution, dropwise adding a few drops of the mixed solution (the mixed solution is the mixed solution of bromobenzene and tetrahydrofuran) at room temperature under the protection of nitrogen gas, contacting a magnesium strip and iodine, and slightly heating to initiate reaction, then continuously (slowly) dropwise adding the mixed solution in an ice water bath (about 0 ℃), and finishing the addition for 1 h; stirring and reacting for 3h at room temperature after the addition is finished to obtain a gray solution, namely a bromobenzene Grignard reagent; then adding 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane (prepared by synthesizing the 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane) and stirring for reacting for 5 hours at the temperature of 50 ℃ to obtain white slurry;
c. separation and purification: cooling the obtained white slurry to room temperature, adding 3M (namely 3mol/L) of dilute hydrochloric acid (the amount of the added dilute hydrochloric acid is enough to react the rest magnesium sheets in the reaction) to quench the redundant Grignard reagent, extracting with 20mL of petroleum ether (preferably petroleum ether with a boiling range of 60-90 ℃), extracting for 3 times, combining organic phases, washing with dilute hydrochloric acid, sodium bicarbonate aqueous solution and water in sequence, adding anhydrous sodium sulfate for drying for 3 hours, concentrating and removing (most) solvent by (rotary) evaporation (instrument) to obtain light yellow liquid, and then performing silica gel column chromatography to obtain the polymerized monomer 1, 3-dimethyl-1, 3-diphenyldisilylobutane (DMDPB) (after silica gel column chromatography (300-400 meshes) and petroleum ether as a developing agent and concentrating and removing the solvent by rotary evaporator).
Example 11:
the preparation method of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane comprises the following steps of:
a. preparing materials: taking 0.013g of iodine, 1.64g of magnesium, 9.076g (0.058mol) of bromobenzene, 6.73g (0.029mol) of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane (preferably prepared according to the molar ratio of bromobenzene: 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane of 2: 1) and tetrahydrofuran for later use;
b. reaction: adding iodine and magnesium into a reactor, vacuumizing and filling nitrogen; diluting bromobenzene in 25mL tetrahydrofuran to obtain a mixed solution, dropwise adding a few drops of the mixed solution (the mixed solution is the mixed solution of bromobenzene and tetrahydrofuran) at room temperature under the protection of nitrogen gas, contacting a magnesium strip and iodine, and slightly heating to initiate reaction, then continuously (slowly) dropwise adding the mixed solution in an ice water bath (about 0 ℃), and finishing the addition for 2 hours; after the addition is finished, stirring and reacting for 2h at room temperature (the optimal reaction time is 2h) to obtain a gray solution, namely the bromobenzene Grignard reagent; then adding 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane (prepared by synthesizing the 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane) and stirring for reacting for 3 hours at the temperature of 60 ℃ to obtain white slurry;
c. separation and purification: cooling the obtained white slurry to room temperature, adding 3M (namely 3mol/L) of dilute hydrochloric acid (the amount of the added dilute hydrochloric acid is enough to react the rest magnesium sheets in the reaction) to quench the redundant Grignard reagent, extracting with 20mL of petroleum ether (preferably petroleum ether with a boiling range of 60-90 ℃), extracting for 3 times, combining organic phases, washing with dilute hydrochloric acid, sodium bicarbonate aqueous solution and water in sequence, adding anhydrous sodium sulfate for drying for 4 hours, concentrating and removing (most) solvent by (rotary) evaporation (instrument) to obtain light yellow liquid, and performing silica gel column chromatography to obtain (silica gel column chromatography (300-400 meshes), wherein the petroleum ether is a developing agent, and the rotary evaporator is used for concentrating and removing the solvent) to obtain the polymeric monomer 1, 3-dimethyl-1, 3-diphenyldisilylobutane (DMDPB);
example 12:
the preparation method of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane comprises the following steps:
a. synthesis of chloromethyl methyl isopropyloxysilane:
the reaction is carried out in a 250mL three-mouth flask of a reactor provided with a magnetic stirrer, and three mouths are respectively connected with a Synthware double-row pipe vacuum gas distributor, a reflux condenser pipe provided with an oil seal and a constant pressure dropping funnel; after checking whether the reactor has a gas leakage, vacuum is applied and the reactor is repeatedly heated (avoiding the interface) using a heating gun to remove water vapor (H) that may be present in the reactor system2O), carbon dioxide (CO)2) Oxygen (O)2) And other impurities that may be present; then introducing nitrogen into the system to fill the whole reactor; the steps of vacuumizing and filling nitrogen are repeatedly operated for three times, so that no water, carbon dioxide, oxygen and other impurities possibly existing in the reaction system are ensured; after the apparatus was cooled down, the flask was placed in an ice-water bath, and 22.89g (17.82mL,0.14mol) (molar ratio of chloromethylmethyldichlorosilane: isopropanol 1.1:1) of chloromethylmethyldichlorosilane was added to the reactor flask under protection of nitrogen gas; adding 7.8g (10mL,0.13mol) of isopropanol into a constant-pressure dropping funnel, and dropping into the reactor for 3h (slowly); after the dropwise addition is finished, continuously reacting for 1h at room temperature; introducing nitrogen gas directly in the whole reaction process to take away hydrogen chloride gas generated in the reaction process; the mixed liquid keeps colorless and transparent in the reaction process, and water mist appears on the inner wall of the constant-pressure dropping funnel along with the reaction; after the reaction is finished, carrying out reduced pressure distillation on the solution after the reaction, and collecting fractions (the temperature is 55-60 ℃ and the pressure is 0.4-0.5 Torr) to obtain colorless transparent liquid, namely the prepared chloromethyl methyl isopropyloxy chlorosilane; the yield is 60.8%;
b. synthesis of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilacyclobutane:
(this process is carried out according to the "reverse addition method" proposed by Kriner); in a 50mL two-neck round bottom flask of a reactor (provided with a magnetic stirrer, a reflux condenser tube, a constant pressure dropping funnel, a Synthware double-row tube vacuum gas distributor and an oil seal), after checking that the reactor has no gas leakage, 1.64g (0.068mol) (the mass of the magnesium sheet can be about 20-1 times excessive and is 1.64-2.78 g) of magnesium (sheet which is polished smooth and cut by sand paper) and a little iodine (0.011-0.013 g) are added. The reactor was evacuated and heated repeatedly using a heat gun to remove water vapor (H) that may be present in the reactor system2O), carbon dioxide (CO)2) Oxygen (O)2) And other impurities that may be present; then introducing nitrogen into the system to fill the whole reactor; the steps of vacuumizing and filling nitrogen are repeatedly operated for three times, so that no water, carbon dioxide, oxygen and other impurities possibly existing in the reaction system are ensured; after the system is cooled to room temperature, adding 5mL of tetrahydrofuran (THF for short) and 0.3mL of dibromoethane activated magnesium strips into a flask of the reactor under the condition of introducing nitrogen for protection; taking 10g (0.057mol) of chloromethyl methyl isopropoxy chlorosilane prepared in the step a, and diluting the chloromethyl methyl isopropoxy chlorosilane in 26mL of tetrahydrofuran to obtain a mixed solution (ensuring that the mass percentage concentration of the chloromethyl methyl isopropoxy chlorosilane is not lower than 30%); under the protection of nitrogen and at room temperature, a few drops of mixed liquor are dripped to contact with magnesium (strips) and iodine to initiate reaction, the solution is rapidly changed from yellow to colorless and then changed into gray, the solvent of the system is slightly refluxed, and the system is obviously heated from the bottom of a round-bottom flask; then moving the system into an ice-water bath (about 0 ℃), continuously and slowly dripping the mixed solution for 1.5h, moving the system into room temperature after finishing addition, stirring for reaction for 2h, continuously reacting for 2h at 50 ℃, continuously increasing the viscosity of the system in the reaction process, and supplementing THF to ensure that the system can be normally stirred; after the reaction is finished, carrying out reduced pressure distillation on the solution after the reaction to collect a fraction with the temperature of 50-55 ℃ and the pressure of 0.4-0.5 Torr to obtain a colorless transparent liquid, namely the prepared 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilicon cyclobutane; the yield is 51.2%;
c. synthesis of polymerized monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane:
a reactor 50mL of two-neck round-bottom flask is adopted, a small amount of (0.011-0.013 g) iodine (in a screw plug hole of a constant pressure dropping funnel) and (polished smooth and sheared by sand paper) 1.64g (0.068mol) magnesium (sheet mass can be excessive by about 20-1 times and is 1.64-2.78 g) are added into the reactor 50mL of two-neck round-bottom flask, the operation of vacuumizing and nitrogen filling is repeated three times, after the temperature of the whole reactor is reduced to room temperature, 10.58g (0.058mol) of 4-bromobenzene benzocyclobutene (1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilicon cyclobutane is weighed according to the molar ratio of 2: 1) and diluted into 27mL of tetrahydrofuran (THF for short) to obtain a reaction liquid, the reaction liquid is transferred into the dropping funnel, under the protection of nitrogen gas, a few drops of mixed liquid (namely, of the mixed liquid of benzocyclobutene and tetrahydrofuran, and iodine are added into the dropping funnel at room temperature to initiate a reaction strip, the solution is changed into gray after being changed from yellow to colorless, the solvent of the system is slightly refluxed, and the system is obviously heated from the bottom of the round-bottom flask of the reactor; then moving the system into an ice-water bath (about 0 ℃), continuously and slowly dripping the solution (the solution is a mixed solution of benzocyclobutene and tetrahydrofuran) under the condition of the ice-water bath, stirring for reaction, and finishing the addition within 1.5 hours; after the addition is finished, the system is moved to room temperature, and stirring reaction is carried out for 2 hours to obtain a gray solution, namely the Grignard reagent of the 4-bromobenzocyclobutene. Then 6.73g (0.029mol) (charged in a 1:2 molar ratio of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilacyclobutane to benzocyclobutene) of the 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilacyclobutane prepared in step b was added and stirred at 40 ℃ for 4h to react and obtain a white slurry;
separation and purification: after the reaction is finished, cooling the obtained white slurry to room temperature, adding 3M (namely 3mol/L) of dilute hydrochloric acid (the amount of the added dilute hydrochloric acid is enough to enable the magnesium sheets remained in the reaction to be reacted completely) to quench the redundant Grignard reagent, extracting with 20mL of petroleum ether (petroleum ether with the boiling range of 60-90 ℃), extracting for 3 times, combining organic phases, washing with dilute hydrochloric acid, sodium bicarbonate aqueous solution and water in sequence, adding anhydrous sodium sulfate, drying for 4 hours (drying for 3-4 hours), concentrating by a rotary evaporator to remove (most of) the solvent to obtain light yellow liquid, performing silica gel column chromatography (300-400 meshes), using petroleum ether as a developing agent, and performing concentration by a rotary evaporator to remove a solvent) to obtain a benzocyclobutene polycarbosilane polymer monomer (I) -1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilicon cyclobutane (DMDBDSCB);
the benzocyclobutene polycarbosilane polymerization monomer (I) is characterized in that: colorless transparent crystals, the structure is characterized as follows:
1H NMR(600MHz,CDCl3)δ(ppm):7.70(d,1H,ArH),7.63(d,1H,ArH),7.56(d,1H,ArH),7.47(s,1H,ArH),7.29(d,1H,ArH),7.24(d,1H,ArH),3.41-3.36(d,8H,-CH2CH2-),0.53(s,6H,Si-CH3),0.42(s,4H,SiCH2Si).；
13C NMR(151MHz,CDCl3)δ(ppm):121-148(C6H5),29.94(s,-CH2CH2-),29.90(s,-CH2CH2-),29.83(s,-CH2CH2-),29.79(s,-CH2CH2-),2.37(s,SiCH2Si),2.32(s,SiCH2Si),1.69(s,Si-CH3),1.63(s,Si-CH3).。
example 13:
4. the preparation method of the polymethylbenzocyclobutene methylene silane is characterized by comprising the following steps:
a. preparing materials: taking 2.9mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane as a raw material; taking a catalyst chloroplatinic acid, diluting the chloroplatinic acid in tetrahydrofuran, and preparing tetrahydrofuran solution of the chloroplatinic acid with the concentration of 0.025M (namely 0.025 mol/L);
b. drying an anaerobic tube (the anaerobic tube is used as a reactor and is mainly used for reactions with high requirements on water and oxygen absence) of the reactor, vacuumizing the anaerobic tube of the reactor after a magnetic stirrer is arranged in the anaerobic tube of the reactor, heating the anaerobic tube by using a heating gun to remove water, oxygen, carbon dioxide and other impurities possibly existing in a reactor system, and then introducing nitrogen to fill the whole reactor system; the operations of vacuumizing and filling nitrogen are repeated for three times to ensure that no water, oxygen, carbon dioxide and other impurities exist in the reaction system; after the whole reactor is cooled to room temperature in a nitrogen atmosphere, an injector is used for anaerobic reaction1, 3-dimethyl-1, 3-dibenzocyclobutenyldisilacyclobutane (abbreviated as DMDDSCB) (2.9mmol) is injected into the tube according to the molar ratio of 1, 3-dimethyl-1, 3-dibenzocyclobutenyldisilacyclobutane monomer to chloroplatinic acid catalyst of 1: 4.3X 10-4Charge), 50 μ L (catalyst chloroplatinic acid: monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane molar ratio is 4.3X 10-41 feeding) reacting the tetrahydrofuran solution of chloroplatinic acid at 100 ℃ for 24 hours, and obviously increasing the viscosity of the system to obtain reacted liquid;
c. separation and purification: and c, subjecting the reacted liquid obtained in the step b to column chromatography, wherein the specific method comprises the following steps: from bottom to top, the column is filled with 2g of diatom powder, 2g of diatomite and 1g of 100-mesh 200-mesh alumina as a stationary phase, toluene as an eluent, the liquid obtained by elution is distilled and concentrated to remove the eluent to obtain a colorless liquid, the colorless liquid is precipitated in ethanol (the specific method is that the colorless liquid is dripped into four times of volume of absolute ethyl alcohol, the solid is precipitated in ethanol and filtered to obtain a solid, the method is the prior art, the solid can be dissolved by proper amount of toluene and dripped into four times of volume of absolute ethyl alcohol, the solid is precipitated in ethanol and filtered to obtain a solid, the process can be repeated for 3 times to remove impurities and low molecular weight polymers), the solid is dried (preferably placed in a 50 ℃ vacuum drying box for drying for 15 hours), the sealed storage is carried out, the yield is calculated by weighing to be 84%, thus obtaining polycarbosilane linear homopolymer, namely poly (methyl benzocyclobutene methylene silane) (PMBSM for short) (II);
the linear polycarbosilane homopolymer (d) is characterized in that: white viscous oil, structure characterized as follows:
1H NMR(600MHz，CDCl3)δ(ppm):0.0-0.1(multi),3.1-3.4(multi),7.1-7.4(br,multi)；
13C NMR(151MHz,CDCl3)δ(ppm):-0.24,0.05,6.0,6.2,6.4,29.7,29.8，127.8,128.8,134.1,141.4.；
infrared Spectrum IR (KBr coated, cm)-1)：3066,2955,2899,2861,1588,1457，1250,1050,733,698。
Example 14:
the preparation method of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane comprises the following steps:
a. the method comprises the following steps of (1) drying an anaerobic tube (the anaerobic tube is used as a reactor and is mainly used for reactions with high requirements on anhydrous oxygen-free) of the reactor by taking chloroplatinic acid (the concentration of the chloroplatinic acid diluted in tetrahydrofuran is 0.025M (namely 0.025mol/L)) as a catalyst, vacuumizing the anaerobic tube after the anaerobic tube is filled with a magnetic stirrer, heating the anaerobic tube by using a heating gun to remove water, oxygen, carbon dioxide and other impurities possibly existing in a reactor system, and then introducing nitrogen to fill the whole reactor system; the operations of vacuumizing and filling nitrogen are repeated for three times to ensure that no water, oxygen, carbon dioxide and other impurities exist in the reaction system; after the whole reactor is cooled to room temperature in a nitrogen atmosphere, 1, 3-dimethyl-1, 3-dibenzocyclobutenyldisilacyclobutane (DMDBDSCB for short) is injected into an anaerobic tube by using an injector (according to the molar ratio of 1, 3-dimethyl-1, 3-dibenzocyclobutenyldisilacyclobutane monomer to DMDPDSB to chloroplatinic acid serving as a catalyst of 1:1: 8.6X 10-4Feed) (0.6mmol), DMDPDSBCB (5.4mmol) (monomer DMDPDSBCB: 1, 3-dimethyl-1, 3-dibenzocyclobutenyldisilacyclobutane: catalyst chloroplatinic acid molar ratio 1:1: 8.6X 10-4Charge), 100 μ L (catalyst chloroplatinic acid: the molar ratio of the monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane to DMDPDSBCB is 8.6X 10-41:1) reacting the chloroplatinic acid at 100 ℃ for 24 hours, and obviously increasing the viscosity of the system to obtain reacted liquid;
the DMDPDSB is 1, 3-dimethyl-1, 3-diphenyldisilylocyclobutane;
b. separation and purification: subjecting the reacted liquid obtained in the step a to column chromatography, sequentially filling 4g of diatom powder, 4g of kieselguhr and 2g of 100-200-mesh alumina serving as a stationary phase and toluene serving as an eluent into the column, distilling and concentrating the eluted liquid to remove the eluent to obtain a colorless liquid, precipitating the colorless liquid in ethanol (the specific method is that the colorless liquid is dripped into four times of volume of absolute ethanol, a solid is precipitated in the ethanol, and filtering to obtain a solid, the solid can be dissolved in a proper amount of toluene, dripped into four times of volume of absolute ethanol, the solid is precipitated in the ethanol, and filtering to obtain a solid, the process can be repeated for 3 times to remove impurities and low molecular weight polymers), and drying for 15 hours in a vacuum drying box at 50 ℃ to obtain the polycarbosilane linear copolymer polymethylphenylsilane/polymethylbenzocyclobutenylidene methylsilylene Alkane (PMPSM-co-PMBSM) (III) is stored in a sealing way, the weighed and calculated yield is 86 percent, and the actual mol content of benzocyclobutene in the resin is 9.4 percent.
The basic characteristics of the polycarbosilane linear copolymer are as follows: a white viscous oil; the structure is characterized as follows:
1H NMR(600MHz,CDCl3)δ(ppm):0.0-0.2(multi),3.1-3.4(multi),7.1-7.6(br,multi).；
13C NMR(151MHz,CDCl3)δ(ppm):-0.27,0.07,6.0,6.2,6.5,29.8,29.9,127.4,128.6,134.2,141.3.；
infrared Spectrum IR (KBr coated, cm)-1)：3024,2955,2910,2849,1588,1456,1253,1050,735,698.。
Example 15:
in the preparation method of the polymethylphenyl methylene silane/polymethylbenzocyclobutene methylene silane, the synthesis method of the polymerized monomer 1, 3-dimethyl-1, 3-diphenyl disilicon cyclobutane (DMDPDSB) is as follows:
a. adopting an anhydrous anaerobic reactor 50mL two-neck round-bottom flask, adding one particle of iodine (0.011-0.013 g) (in a screw plug hole of a constant pressure dropping funnel) and 1.64g (0.068mol) (the mass of the magnesium sheet can be excessive by about 20-1 times and is 1.64-2.78 g) of magnesium (polished smooth and sheared by sand paper), repeating the operations of vacuumizing and filling nitrogen for three times until the temperature of the whole reactor is reduced to room temperature, taking 9.076g (0.058mol) (according to the molar ratio of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane as 2:1 feeding) of bromobenzene, diluting the bromobenzene in 25mL tetrahydrofuran to obtain a mixed solution, transferring the mixed solution into the constant pressure dropping funnel, and dropwise adding a few drops of the mixed solution (namely the mixed solution of bromobenzene and tetrahydrofuran) to contact with the magnesium strip and the iodine at room temperature to initiate reaction, the solution quickly changes from yellow to colorless and then changes into gray, the solvent of the system slightly refluxes, and the system obviously feels exothermic from the bottom of the round-bottom flask; then the system is moved to an ice water bath (about 0 ℃), the mixed solution is continuously and slowly dripped, and the addition is finished within 1.5 hours; after the addition is finished, moving the system to room temperature, and stirring for reaction for 2 hours to obtain a gray solution, namely a Grignard reagent of bromobenzene; 6.73g (0.029mol) of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylobutane prepared before (obtained by synthesizing 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylobutane as described above) the molar ratio of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylobutane to bromobenzene was added thereto, and then stirred at 50 ℃ for 4 hours to obtain a white slurry;
b. separation and purification: cooling the obtained white slurry to room temperature, adding 3M (namely 3mol/L) of dilute hydrochloric acid (the amount of the added dilute hydrochloric acid is enough to react the rest magnesium sheets in the reaction) to quench the redundant Grignard reagent, extracting with 20mL of petroleum ether (preferably petroleum ether with a boiling range of 60-90 ℃), extracting for 3 times, combining organic phases, washing with dilute hydrochloric acid, sodium bicarbonate aqueous solution and water in sequence, adding anhydrous sodium sulfate to dry for 3.5h, concentrating and removing (most) solvent by (rotary) evaporation (instrument) to obtain light yellow liquid, and performing silica gel column chromatography to obtain a polymerized monomer 1, 3-dimethyl-1, 3-diphenyldisilicon cyclobutane (DMDPSCB) [ silica gel column chromatography (300-400 meshes), petroleum ether is a developing agent, and the solvent is removed by rotary evaporator concentration ];
the basic characteristics of the polymerized monomer 1, 3-dimethyl-1, 3-diphenyldisilylocyclobutane (DMDPDSBCB): a colorless transparent liquid; the structure is characterized as follows:
1H NMR(600MHz,CDCl3)δ(ppm):7.66-7.63(m,2H,ArH),7.56(d,2H,ArH),7.39(d,3H,ArH),7.34-7.31(m,3H,ArH),0.58(s,6H,Si-CH3),0.46(s,4H,SiCH2Si).；
13C NMR(151MHz,CDCl3)δ(ppm):127-142(C6H5),2.41(s,SiCH2Si),2.49(s,SiCH2Si),1.47(s,Si-CH3),1.50(s,Si-CH3).。
in the above embodiment: all the raw materials are commercially available products.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the parts by mass (by weight) may all be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, pressure, concentration, etc.) and the amounts of the components in each step are within the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above embodiments are the same as the prior art.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (4)
1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilicon cyclobutane, characterized in that said benzocyclobutene polycarbosilane polymeric monomer has the chemical structural formula shown in formula (i):
the preparation method of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane is characterized by comprising the following steps:
a. synthesis of chloromethyl methyl isopropyloxysilane:
in an ice-water bath, 22.89g of chloromethyl methyl dichlorosilane is added into a reactor under the protection of nitrogen; adding 7.8g of isopropanol into a constant-pressure dropping funnel, and dropping into the reactor for 2-4 hours; after the dropwise addition is finished, continuously reacting for 1-2 h at room temperature; after the reaction is finished, carrying out reduced pressure distillation on the solution after the reaction, and collecting fractions under the conditions that the temperature is 55-60 ℃ and the pressure is 0.4-0.5 Torr to obtain colorless transparent liquid, namely the prepared chloromethyl methyl isopropyloxy chlorosilane;
b. synthesis of 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilacyclobutane:
adding 1.64-2.78 g of magnesium and 0.011-0.013 g of iodine into a reactor; adding 5-10 mL of tetrahydrofuran and 0.1-0.3 mL of dibromoethane into a reactor under the protection of nitrogen; taking 10g of chloromethyl methyl isopropyloxy chlorosilane prepared in the step a, and diluting the chloromethyl methyl isopropyloxy chlorosilane in 26mL of tetrahydrofuran to obtain a mixed solution; dropwise adding a few drops of mixed liquor at room temperature under the protection of nitrogen gas, contacting with magnesium and iodine to initiate reaction, then transferring the system to an ice water bath, continuously dropwise adding the mixed liquor for 1-2 hours, transferring to room temperature after adding, stirring for reaction for 2-3 hours, and then continuously reacting for 2-3 hours at 50-60 ℃; after the reaction is finished, carrying out reduced pressure distillation on the solution after the reaction, and collecting fractions with the temperature of 50-55 ℃ and the pressure of 0.4-0.5 Torr to obtain colorless transparent liquid, namely the prepared 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane;
c. synthesis of polymerized monomer 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane:
adding 0.011-0.013 g of iodine and 1.64-2.78 g of magnesium into a reactor; weighing 10.58g of 4-bromobenzocyclobutene, diluting the mixture in 27mL of tetrahydrofuran to obtain a mixed solution, dropwise adding a few drops of the mixed solution at room temperature under the protection of nitrogen gas to contact magnesium and iodine to initiate reaction, then continuously dropwise adding the mixed solution under the condition of ice-water bath, stirring for reaction, and finishing the addition for 1-2 hours; after the addition is finished, moving the system to room temperature, and stirring for reaction for 2-3 h to obtain a Grignard reagent of 4-bromobenzocyclobutene; adding 6.73g of the 1, 3-diisopropoxy-1, 3-dimethyl-1, 3-disilylocyclobutane prepared in the step b, and stirring and reacting at the temperature of 40-60 ℃ for 3-5 hours to obtain white slurry;
separation and purification: after the reaction is finished, cooling the obtained white slurry to room temperature, extracting with 20mL of petroleum ether for 3 times, combining organic phases, washing with dilute hydrochloric acid and sodium bicarbonate aqueous solution in sequence, adding anhydrous sodium sulfate, drying for 3-4 h, removing the solvent through evaporation and concentration to obtain light yellow liquid, and performing silica gel column chromatography to obtain 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilicon cyclocyclobutane;
the basic characteristics of the 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane are as follows: colorless transparent crystals, the structure is characterized as follows:
1H NMR(600MHz,CDCl3)δ(ppm):7.70(d,1H,ArH),7.63(d,1H,ArH),7.56(d,1H,ArH),7.47(s,1H,ArH),7.29(d,1H,ArH),7.24(d,1H,ArH),3.41-3.36(d,8H,-CH2CH2-),0.53(s,6H,Si-CH3),0.42(s,4H,SiCH2Si).；
13C NMR(151MHz,CDCl3)δ(ppm):121-148(C6H5),29.94(s,-CH2CH2-),29.90(s,-CH2CH2-),29.83(s,-CH2CH2-),29.79(s,-CH2CH2-),2.37(s,SiCH2Si),2.32(s,SiCH2Si),1.69(s,Si-CH3),1.63(s,Si-CH3)。
3. the polymethylbenzocyclobutene methylene silane is characterized in that the benzocyclobutene polycarbosilane resin has a chemical structural formula shown in a formula (II):
the molecular weight of the polymethylbenzocyclobutene methylene silane (II) is 30000-40000.
4. The preparation method of the polymethylbenzocyclobutene methylene silane is characterized by comprising the following steps:
a. preparing materials: taking 2.9mmol of 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane as a raw material; taking a catalyst chloroplatinic acid, diluting the chloroplatinic acid in tetrahydrofuran, and preparing tetrahydrofuran solution with the concentration of 0.025M chloroplatinic acid for later use;
b. reaction: under the protection of nitrogen, injecting 1, 3-dimethyl-1, 3-dibenzocyclobutenyl disilylocyclobutane and 50 mu L tetrahydrofuran solution of chloroplatinic acid into a reactor, and reacting at the temperature of 80-100 ℃ for 18-24 h to obtain reacted liquid;
c. separation and purification: c, subjecting the reacted liquid obtained in the step b to column chromatography, distilling and concentrating the eluted liquid to remove the eluent to obtain colorless liquid, precipitating the colorless liquid in ethanol, and drying the obtained solid to obtain the polymethylbenzocyclobutene methylene silane (II);
the polymethyl benzocyclobutene radical methylene silicane has the following basic characteristics: white viscous oil, structure characterized as follows:
1H NMR(600MHz，CDCl3)δ(ppm):0.0-0.1(multi),3.1-3.4(multi),7.1-7.4(br,multi)；
13C NMR(151MHz,CDCl3)δ(ppm):-0.24,0.05,6.0,6.2,6.4,29.7,29.8，127.8,128.8,134.1,141.4；
infrared Spectrum IR (KBr coated, cm)-1)：3066,2955,2899,2861,1588,1457，1250,1050,733,698。
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| Preparation and Thermal Properties of Asymmetrically Substituted Poly(silylenemethylene)s;Q. H. SHEN等,;《Journal of Polymer Science: Part A: Polymer Chemistry》;20001201;3193-3205页 * |
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