CN101899156B - Preparation method of multichain trapezoidal polyalkyl silsesquioxane - Google Patents
Preparation method of multichain trapezoidal polyalkyl silsesquioxane Download PDFInfo
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- CN101899156B CN101899156B CN201010170818XA CN201010170818A CN101899156B CN 101899156 B CN101899156 B CN 101899156B CN 201010170818X A CN201010170818X A CN 201010170818XA CN 201010170818 A CN201010170818 A CN 201010170818A CN 101899156 B CN101899156 B CN 101899156B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000967 suction filtration Methods 0.000 claims description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- -1 suction filtration Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 239000005046 Chlorosilane Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 239000005047 Allyltrichlorosilane Substances 0.000 claims description 2
- 229910007926 ZrCl Inorganic materials 0.000 claims description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 2
- ATGKAFZFOALBOF-UHFFFAOYSA-N cyclohexyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCCC1 ATGKAFZFOALBOF-UHFFFAOYSA-N 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011968 lewis acid catalyst Substances 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005053 propyltrichlorosilane Substances 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- SIPHWXREAZVVNS-UHFFFAOYSA-N trichloro(cyclohexyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCCC1 SIPHWXREAZVVNS-UHFFFAOYSA-N 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 claims description 2
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 claims description 2
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000011229 interlayer Substances 0.000 abstract description 4
- 238000004377 microelectronic Methods 0.000 abstract description 4
- 239000002114 nanocomposite Substances 0.000 abstract description 4
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 229920001002 functional polymer Polymers 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000005622 photoelectricity Effects 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 150000003613 toluenes Chemical class 0.000 description 6
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical class CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 208000013403 hyperactivity Diseases 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical class CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000004223 radioprotective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of multichain trapezoidal polyalkyl silsesquioxane, comprising the following steps of making hydrogenalkoxysilanes and chlorsilane which are used as precursors, and carboxylic acid or Lewis acid which is used as catalysts to carry out nonhydrolytic condensation polymerization at the reaction temperature of 0-110 DEG C in an organic solvent. The multichain trapezoidal polyalkyl silsesquioxane has highly regular structure, narrow molecular weight distribution, excellent thermal stability and excellent mechano-mechanical property and can be widely used for lots of special functional polymer materials, nano composite materials, internal interlayer insulating films of a microelectronic device, polymer catalysts and substrates of photoelectricity information high-polymer nonlinear optical materials, and the like. The invention has simple production technology, low energy and time consumption, mild condition, low cost , environment friendliness, and the like and is easy to realize large-scale production and application. The varieties of the molecular weight, lateral groups and terminal groups of the multichain trapezoidal polyalkyl silsesquioxane can be regulated in order to satisfy different application requirements.
Description
Technical field
The present invention relates to the technology of preparing of multichain trapezoidal polyalkyl silsesquioxane.
Background technology
Double-stranded trapezoidal polyalkyl silsesquioxane oxygen alkane (Double-chains ladder polyalkylsilsesquioxanes; Be called for short: LPSQs); Because have inorganic pair of main chain backbone simultaneously and pusher side/end group is arranged in the molecule rank, so, superior heat-stability ability and superior mechanical-mechanical property had; In addition, the LPQSs film-forming properties is good, swelling capacity is lower, radioprotective and dielectric properties are preferable.Can be widely used in the base material of many specific functionality macromolecular materials, nano composite material, the inner interlayer insulating film of microelectronic device, polymer catalyst and optoelectronic information polymer nonlinear optical material etc.In recent years, become one of research focus of organosilicon polymer gradually based on trapezoidal organosilicon macromolecule material, nano composite material, microelectronic device inside interlayer insulating film and the insulating coating etc. that gather silicious sesquioxane of two strands.
Brown and co-worker thereof adopt what is called " balance condensation method " successfully to synthesize double-stranded ladder-like poly-phenyl silsesquioxane first, because used temperature of reaction is higher and the cause of specific reactions mechanism, their ladder structure once was under suspicion.People such as Zhang Rongben propose the deficiency that " progressively coupling polymerization method " overcomes people's method therefors such as Brown, and to obtain the ladder structure of high-regularity, its method feature is need adopt so-called " template molecule " early stage of building-up process: organic diamine.Unno and colleague are initial monomers with the cyclotetrasiloxane tetrol, and the approach that combines through the progressively condensation reaction of chlorosilane " silanol with " and " taking off the benzene chloro " synthesizes the highly trapezoidal silicious sesquioxane that gathers in five rings of regularity.Though above-mentioned these methods can both successfully obtain the comparatively regular trapezoidal silicious sesquioxane that gathers of structure; But all belong to the hydrolytie polycondensation method; Ubiquity reaction monomers hyperactivity, various, the complicated operation of step; Some only is applicable to the silane monomer raw material of special construction, not the production and the application of suitable mass-producing.For this reason, the novel method that needs the preparation multichain trapezoidal polyalkyl silsesquioxane that development technology is easy, reaction is quick, cost is low, efficient is high.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing preparation multichain trapezoidal polyalkyl silsesquioxane technology, provide a kind of simple, cost is low, operation is convenient and the eco-friendly preparation method who is suitable for the suitability for industrialized production multichain trapezoidal polyalkyl silsesquioxane.
To achieve these goals, the present invention adopts following technical scheme:
A kind of preparation method of multichain trapezoidal polyalkyl silsesquioxane, adopting trialkoxy silane, chlorosilane is presoma, is catalyzer with carboxylic acid or Lewis acid, in organic solvent, carries out non-hydrolytic condensation polymerization under 0～110 ℃ of the temperature of reaction and gets.
In above-mentioned preparation method, said trialkoxy silane is preferably one or more the mixture in phenyltrimethoxysila,e, phenyl triethoxysilane, sec.-propyl Trimethoxy silane, sec.-propyl triethoxyl silane, aminopropyl trimethoxysilane, aminopropyl triethoxysilane, ethyl triethoxysilane, ethyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane.
In above-mentioned preparation method, said chlorosilane is preferably one or more the mixture in METHYL TRICHLORO SILANE, ethyl trichlorosilane, propyltrichlorosilan, vinyl trichloro silane, dimethyldichlorosilane(DMCS), tetrachloro silicane, phenyl-trichloro-silicane, allyltrichlorosilane, sec.-propyl trichlorosilane, the cyclohexyl trichlorosilane.
In above-mentioned preparation method, when the trichlorosilane with the trialkoxy silane of 7.1～40 weight parts and 7.5～60 weight parts was presoma, the multichain trapezoidal polyalkyl silsesquioxane of acquisition was suc as formula shown in (I);
Wherein, R
1Or R
2Be methyl, phenyl, sec.-propyl or aminopropyl, R is hydrogen, methyl or ethyl, n=100～200.
When the tetrachloro silicane with the trialkoxy silane of 7.1～60 weight parts and 3.5～40 weight parts was presoma, the multichain trapezoidal polyalkyl silsesquioxane of acquisition was suc as formula shown in (II);
Wherein, R
1Be methyl, phenyl, sec.-propyl or aminopropyl, R is hydrogen, methyl or ethyl, n=100～200.
When the dichlorosilane with the trialkoxy silane of 7.1～60 weight parts and 3.5～40 weight parts was presoma, the multichain trapezoidal polyalkyl silsesquioxane of acquisition was suc as formula shown in (III);
Wherein, R
1Or R
2Be methyl, phenyl, sec.-propyl or aminopropyl, R is hydrogen, methyl or ethyl, n=100～200.
In above-mentioned preparation method, said catalyzer is preferably trichoroacetic acid(TCA), trifluoroacetic acid, AlCl
3, FeCl
3, TiCl
4, ZrCl
4, BCl
3In one or more mixture, consumption is the 0.05-4 weight part.
In above-mentioned preparation method, said organic solvent is preferably one or more the mixture in acetone, hexone, THF, toluene, benzene, 1,4～dioxane, the tetracol phenixin, and consumption is the 100-400 weight part.
The preparation method of above-mentioned multichain trapezoidal polyalkyl silsesquioxane may further comprise the steps:
(1) 0～110 ℃, trialkoxy silane is dissolved in the organic solvent of 65%～95% weight part, after mixing, add carboxylic acid or lewis acid catalyst under the violent stirring;
(2) 0～110 ℃, react after 3～24 hours, slowly drip chlorosilane, dropwise in 3～12 hours scopes;
(3) 0～110 ℃, continue reaction 20～120 hours;
(4) after reaction finishes, suction filtration, filtrating is carried out underpressure distillation, and distillation temperature begins from room temperature earlier; Be not warmed up to 60 ℃ to having when cut flows out, be not warmed up to 80 ℃ again, be warmed up to 110 ℃ at last by the time have when cut flows out; Till no cut flowed out, distillation leftover was used organic solvent dissolution, slowly adds in 400～2000 weight part anhydrous methanols; Obtain white precipitate, suction filtration, filter cake was in 50～110 ℃ of vacuum dryings 12～48 hours.
In order to control product structure; Between above preparing method's step (3) and step (4), increase following steps: the mixing liquid that dropwise adds 2～5 parts by weight of purified water and 35%～5% weight part organic solvent; Dropwise in 3～18 hours; Continue reaction 24～64 hours, water-and-oil separator is installed and is elevated to 100～120 ℃ of reaction 5～10h to temperature of reaction, reaction solution is extremely neutral with saturated NaCl solution washing, anhydrous Na
2SO
4Dry 12～24h.
Compared with prior art, the present invention has following beneficial effect:
Can know by non-hydrolytic condensation polymerization reaction mechanism; Non-hydrolytic condensation polymeric speed of response slowly is easy to control, can regulate and control the reaction between trialkoxy silane and the many chlorosilanes presoma easily: at first, and the sily oxide midbody that generating structure is confirmed; Secondly; Utilize sterically hindered effect, the reaction between regulation and control organoalkoxysilane and the chlorosilane is used to control multichain trapezoid molecular structure.If hydrolysis-condensation reaction is adopted in the second step condensation, then the sily oxide midbody be through can carrying out self-assembly through hydrogen bond between the silicon hydroxyl that hydrolysis reaction generated, thereby forms the multichain trapezoidal polyalkyl silsesquioxane of compound with regular structure.
The multichain trapezoidal polyalkyl silsesquioxane that the present invention makes has height regularity structure; MWD is narrower; Have good thermal stability, machinery-mechanical property simultaneously, can be widely used in the matrix of many specific functionality macromolecular materials, nano composite material, the inner interlayer insulating film of microelectronic device, polymer catalyst and optoelectronic information polymer nonlinear optical material etc.The non-hydrolytic condensation polymerization of the present invention's design; Have that production technique is simple, few during consumption energy consumption, mild condition, preparation cost are low, accomplish scale production easily and characteristics such as application, environmental friendliness; This method also is easy to regulate the kind of the molecular weight, side group and the end group that connect trapezoidal polyalkyl silsesquioxane oxygen alkane more, to satisfy the demand of different application.
Description of drawings
The X-ray diffractogram of the double-stranded trapezoidal polyphenylmethyl base silicious sesquioxane of Fig. 1;
The infrared spectrogram of the double-stranded trapezoidal polyphenylmethyl base silicious sesquioxane of Fig. 2;
The double-stranded trapezoidal polyphenylmethyl base silicious sesquioxane of Fig. 3
29The Si nmr spectrum.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is done further to describe, but be not subject to these embodiment.
Embodiment 1
10 parts of phenyltrimethoxysila,e are dissolved in 100 parts of anhydrous hexones, after magnetic agitation mixes, add 1.5 parts of trichoroacetic acid(TCA)s, 20 ℃ were reacted 5 hours.Then drip the mixed solution of 11 parts of METHYL TRICHLORO SILANEs and 20 parts of anhydrous hexones; Dropwised in 4 hours, continue reaction after 60 hours, underpressure distillation: distillation temperature begins from room temperature earlier; When flowing out, cut is not warmed up to 60 ℃ to having; Be not warmed up to 80 ℃ again by the time have when cut flows out, be warmed up to 110 ℃ at last, till no cut flows out.Distillation leftover slowly splashes in 500 parts of anhydrous methanols and produces a large amount of white precipitates gradually with the dissolving of 50 parts of hexones fully, suction filtration, and filter cake can get white powder polyphenylmethyl base silicious sesquioxane product in 60 ℃ of vacuum dryings 24 hours.The X-ray diffractogram of the double-stranded trapezoidal polyphenylmethyl base silicious sesquioxane product of gained is as shown in Figure 1, and the ir spectra of the double-stranded trapezoidal polyphenylmethyl base silicious sesquioxane product of gained is as shown in Figure 2, the double-stranded trapezoidal polyphenylmethyl base silicious sesquioxane product of gained
29The Si nmr spectrum is as shown in Figure 3.
Embodiment 2
10 parts of phenyltrimethoxysila,e are dissolved in 100 parts of anhydrous hexones, after magnetic agitation mixes, add 1.5 parts of trichoroacetic acid(TCA)s, 10 ℃ were reacted 5 hours.Then drip the mixed solution of 11 parts of METHYL TRICHLORO SILANEs and 15 parts of anhydrous hexones; Dropwised in 4 hours, continue reaction after 60 hours, underpressure distillation: distillation temperature begins from the greenhouse earlier; When flowing out, cut is not warmed up to 60 ℃ to having; Be not warmed up to 80 ℃ again by the time have when cut flows out, be warmed up to 110 ℃ at last, till no cut flows out.Distillation leftover slowly splashes in 500 parts of anhydrous methanols and produces a large amount of white precipitates gradually with the dissolving of 50 parts of toluene fully, suction filtration, and filter cake can get the double-stranded trapezoidal polyphenylmethyl base silicious sesquioxane product of white powder in 60 ℃ of vacuum dryings 36 hours.
Embodiment 3
10 parts of phenyltrimethoxysila,e are dissolved in 100 parts of anhydrous hexones, after magnetic agitation mixes, add 1.5 parts of trichoroacetic acid(TCA)s, 20 ℃ were reacted 5 hours.Then drip the mixed solution of 11 parts of METHYL TRICHLORO SILANEs and 15 parts of anhydrous hexones; Dropwised in 12 hours, continue reaction after 80 hours, underpressure distillation: distillation temperature begins from the greenhouse earlier; When flowing out, cut is not warmed up to 60 ℃ to having; Be not warmed up to 80 ℃ again by the time have when cut flows out, be warmed up to 110 ℃ at last, till no cut flows out.Distillation leftover slowly splashes in 500 parts of anhydrous methanols and produces a large amount of white precipitates gradually with the dissolving of 50 parts of hexones fully, suction filtration, and filter cake can get white powder polyphenylmethyl base silicious sesquioxane product in 60 ℃ of vacuum dryings 48 hours.
Embodiment 4
10 parts of phenyltrimethoxysila,e are dissolved in 100 parts of anhydrous hexones, after magnetic agitation mixes, add 1.5 parts of trichoroacetic acid(TCA)s, 0 ℃ was reacted 5 hours.Then dropwise drip the mixed solution of 11 parts of METHYL TRICHLORO SILANEs and 20 parts of anhydrous hexones; Dropwised in 5 hours, continue reaction after 120 hours, underpressure distillation: distillation temperature begins from the greenhouse earlier; When flowing out, cut is not warmed up to 60 ℃ to having; Be not warmed up to 80 ℃ again by the time have when cut flows out, be warmed up to 110 ℃ at last, till no cut flows out.Distillation leftover with 50 parts of hexone dissolvings fully; Slowly splash in 500 parts of anhydrous methanols and produce a large amount of white precipitates gradually; Suction filtration, filter cake can get the double-stranded trapezoidal polyphenylmethyl base silicious sesquioxane product of white powder in 110 ℃ of vacuum dryings 24 hours.
Embodiment 5
20 parts of aminopropyl trimethoxysilane are dissolved in 150 parts of dry toluenes, after magnetic agitation mixes, add 2 parts of trichoroacetic acid(TCA)s, 20 ℃ were reacted 5 hours.Then dropwise drip the mixed solution of 11 parts of silicon tetrachlorides and 40 parts of dry toluenes; Dropwised in 6 hours, continue reaction after 60 o'clock, underpressure distillation: distillation temperature begins from the greenhouse earlier; When flowing out, cut is not warmed up to 60 ℃ to having; Be not warmed up to 80 ℃ again by the time have when cut flows out, be warmed up to 110 ℃ at last, till no cut flows out.Distillation leftover slowly splashes in 800 parts of anhydrous methanols and produces a large amount of white precipitates gradually with the dissolving of 50 parts of toluene fully, suction filtration, and filter cake can get the trapezoidal aminopropyl silicious sesquioxane product that gathers of white powder three chains in 80 ℃ of vacuum dryings 12 hours.
Embodiment 6
20 parts of cyclohexyl trimethoxy silanes are dissolved in 150 parts of dry toluenes, after magnetic agitation mixes, add 4 parts of trichoroacetic acid(TCA)s, 20 ℃ were reacted 5 hours.Then dropwise drip the mixed solution of 11 parts of diethyl dichlorosilanes and 40 parts of dry toluenes; Dropwised in 6 hours, continue reaction after 60 hours, underpressure distillation: distillation temperature begins from the greenhouse earlier; When flowing out, cut is not warmed up to 60 ℃ to having; Be not warmed up to 80 ℃ again by the time have when cut flows out, be warmed up to 110 ℃ at last, till no cut flows out.Distillation leftover slowly splashes in 800 parts of anhydrous methanols and produces a large amount of white precipitates gradually with the dissolving of 50 parts of toluene fully, suction filtration, and filter cake can get the double-stranded trapezoidal cyclohexyl silicious sesquioxane product that gathers of white powder bridging in 80 ℃ of vacuum dryings 24 hours.
Embodiment 7
Under 20 ℃ of conditions, add successively in 150 parts of dry toluenes after 20 parts of cyclohexyl trimethoxy silanes and 0.05 part of iron trichloride magnetic agitation mix, reacted 4 hours.Drip 11 parts of diethyl dichlorosilanes, 5h dropwises, and 20 ℃ are continued reaction 36h.Drip the mixing liquid of 10 parts of water and 40 parts of toluene, be added dropwise to complete in 12 hours, 20 ℃ are continued reaction 24 hours.Water-and-oil separator is installed and is elevated to 110 ℃ of reaction 5h to temperature of reaction.Suction filtration, filtrating to neutral, adds anhydrous Na with the washing of NaCl saturated aqueous solution
2SO
4Dry 12h.Suction filtration, filtrating is carried out underpressure distillation, and distillation temperature begins from room temperature earlier; Be not warmed up to 60 ℃ to having when cut flows out, be not warmed up to 80 ℃ again, be warmed up to 110 ℃ at last by the time have when cut flows out; Till no cut flowed out, distillation leftover was used organic solvent dissolution, slowly splashes in 800 parts of anhydrous methanols and produces a large amount of white precipitates gradually; Suction filtration, filter cake can get the double-stranded trapezoidal cyclohexyl silicious sesquioxane product that gathers of white powder bridging in 80 ℃ of vacuum dryings 48 hours.
Embodiment 8
Under 20 ℃ of conditions, add 10 parts of methyltrimethoxy silanes and 0.05 part of iron trichloride in 100 parts of dry toluenes successively, after mixing, reacted 8 hours, drip 11 parts of METHYL TRICHLORO SILANEs, 5h dropwises, and 20 ℃ are continued reaction 36h.Drip the mixing liquid of 6 parts of water and 10 parts of toluene, be added dropwise to complete in 8 hours, 20 ℃ are continued reaction 48 hours.Water-and-oil separator is installed, and temperature of reaction is elevated to 100 ℃, reacts 8 hours.Suction filtration, filtrating to neutral, adds anhydrous Na with the washing of NaCl saturated aqueous solution
2SO
4Dry 24h.Suction filtration, filtrating is carried out underpressure distillation, and distillation temperature begins from room temperature earlier; Be not warmed up to 60 ℃ to having when cut flows out, be not warmed up to 80 ℃ again, be warmed up to 110 ℃ at last by the time have when cut flows out; Till no cut flowed out, distillation leftover was used organic solvent dissolution, and filtrating slowly splashes in 500 parts of anhydrous methanols and produces a large amount of white precipitates gradually; Suction filtration, filter cake can get the double-stranded trapezoidal methyl silsesquioxane product that gathers of white powder in 110 ℃ of vacuum dryings 24 hours.
Claims (9)
1. the preparation method of a multichain trapezoidal polyalkyl silsesquioxane is characterized in that may further comprise the steps:
(1) 0～110 ℃, trialkoxy silane is dissolved in the organic solvent of 65%～95% weight part, after mixing, add carboxylic acid or lewis acid catalyst under the violent stirring;
(2) 0～110 ℃, react after 3～24 hours, slowly drip chlorosilane, dropwise in 3～12 hours scopes;
(3) 0～110 ℃, continue reaction 20～120 hours;
(4) after reaction finishes, suction filtration, filtrating is carried out underpressure distillation, and distillation temperature begins from room temperature earlier; Be not warmed up to 60 ℃ to having when cut flows out, be not warmed up to 80 ℃ again, be warmed up to 110 ℃ at last by the time have when cut flows out; Till no cut flowed out, distillation leftover was used organic solvent dissolution, slowly adds in 400～2000 weight part anhydrous methanols; Obtain white precipitate, suction filtration, filter cake was in 50～110 ℃ of vacuum dryings 12～48 hours.
2. preparation method according to claim 1 is characterized in that said trialkoxy silane is one or more the mixture in phenyltrimethoxysila,e, phenyl triethoxysilane, sec.-propyl Trimethoxy silane, sec.-propyl triethoxyl silane, aminopropyl trimethoxysilane, aminopropyl triethoxysilane, ethyl triethoxysilane, ethyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane.
3. preparation method according to claim 1 is characterized in that said chlorosilane is one or more the mixture in METHYL TRICHLORO SILANE, ethyl trichlorosilane, propyltrichlorosilan, vinyl trichloro silane, dimethyldichlorosilane(DMCS), tetrachloro silicane, phenyl-trichloro-silicane, allyltrichlorosilane, sec.-propyl trichlorosilane, the cyclohexyl trichlorosilane.
4. according to claim 1 or 2 or 3 described preparing methods, it is characterized in that: when the trichlorosilane with the trialkoxy silane of 7.1～40 weight parts and 7.5～60 weight parts was presoma, the multichain trapezoidal polyalkyl silsesquioxane of acquisition was suc as formula shown in (I);
Wherein, R
1Or R
2Be methyl, phenyl, sec.-propyl or aminopropyl, R is hydrogen, methyl or ethyl, n=100-200.
5. according to claim 1 or 2 or 3 described preparing methods, it is characterized in that: when the tetrachloro silicane with the trialkoxy silane of 7.1～60 weight parts and 3.5～40 weight parts was presoma, the multichain trapezoidal polyalkyl silsesquioxane of acquisition was suc as formula shown in (II);
Wherein, R
1Be methyl, phenyl, sec.-propyl or aminopropyl, R is hydrogen, methyl or ethyl, n=100～200.
6. according to claim 1 or 2 or 3 described preparing methods; It is characterized in that: when the dichlorosilane with the trialkoxy silane of 7.1～60 weight parts and 3.5～40 weight parts was presoma, the multichain trapezoidal polyalkyl silsesquioxane of acquisition was suc as formula shown in (III);
Wherein, R
1Or R
2Be methyl, phenyl, sec.-propyl or aminopropyl, R is hydrogen, methyl or ethyl, n=100～200.
7. preparation method according to claim 1 is characterized in that said catalyzer is trichoroacetic acid(TCA), trifluoroacetic acid, AlCl
3, FeCl
3, TiCl
4, ZrCl
4, BCl
3In one or more mixture, consumption is 0.05～4 weight part.
8. preparation method according to claim 1; It is characterized in that said organic solvent is acetone, hexone, THF, toluene, benzene, 1; The mixture of one or more in 4-dioxane, the tetracol phenixin, consumption are 100～400 weight parts.
9. preparation method according to claim 1; It is characterized in that increasing following steps between step (3) and the step (4): the mixing liquid that dropwise adds 2～5 parts by weight of purified water and 35%～5% weight part organic solvent; Dropwise in 3～18 hours; Continue reaction 24～64 hours, water-and-oil separator is installed and is elevated to 100～120 ℃ of reaction 5～10h to temperature of reaction, reaction solution is extremely neutral with saturated NaCl solution washing, anhydrous Na
2SO
4Dry 12～24h.
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| CN104262629B (en) * | 2014-09-28 | 2017-01-25 | 吉林大学 | Oligomerized methyl trapezoid silsesquioxane and preparation method thereof |
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| CN108948359B (en) * | 2018-08-30 | 2020-06-02 | 北京理工大学 | Trapezoidal polysilsesquioxane containing phenyl and vinyl at same time and preparation method thereof |
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