CN107880267B - Siloxane-bridged-group trapezoidal polysiloxane blocked by siloxane-bridged silane and preparation method thereof - Google Patents
Siloxane-bridged-group trapezoidal polysiloxane blocked by siloxane-bridged silane and preparation method thereof Download PDFInfo
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- CN107880267B CN107880267B CN201711146924.2A CN201711146924A CN107880267B CN 107880267 B CN107880267 B CN 107880267B CN 201711146924 A CN201711146924 A CN 201711146924A CN 107880267 B CN107880267 B CN 107880267B
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- siloxane
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- silane
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- -1 polysiloxane Polymers 0.000 title claims abstract description 234
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 116
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 77
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 230000002195 synergetic effect Effects 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 43
- 125000004122 cyclic group Chemical group 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 21
- 125000004429 atom Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 125000004423 acyloxy group Chemical group 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003456 ion exchange resin Substances 0.000 claims description 13
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 125000004437 phosphorous atom Chemical group 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000003623 transition metal compounds Chemical class 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 125000000068 chlorophenyl group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 15
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- 239000000413 hydrolysate Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 60
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- 238000010992 reflux Methods 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- 238000010907 mechanical stirring Methods 0.000 description 20
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 18
- 230000009477 glass transition Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 13
- 230000003472 neutralizing effect Effects 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- 229960001701 chloroform Drugs 0.000 description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 8
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 239000002981 blocking agent Substances 0.000 description 5
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical group C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000007257 deesterification reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- UKSWSALBYQIBJN-UHFFFAOYSA-N dihydroxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](O)(O)CC(C)C UKSWSALBYQIBJN-UHFFFAOYSA-N 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- WLCHZGMNFDVFED-UHFFFAOYSA-N ditert-butyl(dihydroxy)silane Chemical compound CC(C)(C)[Si](O)(O)C(C)(C)C WLCHZGMNFDVFED-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920001558 organosilicon polymer Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000000646 scanning calorimetry Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- DEZDKWLZZLEVST-UHFFFAOYSA-N tetrabutyl(hydroxy)-$l^{5}-phosphane Chemical compound CCCCP(O)(CCCC)(CCCC)CCCC DEZDKWLZZLEVST-UHFFFAOYSA-N 0.000 description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- YNEHCIJMLGCQIS-UHFFFAOYSA-N 2-methylprop-2-enoic acid;trimethoxy(propyl)silane Chemical compound CC(=C)C(O)=O.CCC[Si](OC)(OC)OC YNEHCIJMLGCQIS-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 240000000231 Ficus thonningii Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HFQKWOKZJDWSQX-UHFFFAOYSA-N [SiH2](O)O.C=CC.C=CC Chemical compound [SiH2](O)O.C=CC.C=CC HFQKWOKZJDWSQX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BSNASBXELXDWSZ-UHFFFAOYSA-N dihydroxy(dipropyl)silane Chemical compound CCC[Si](O)(O)CCC BSNASBXELXDWSZ-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004405 heteroalkoxy group Chemical group 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 125000005553 heteroaryloxy group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KDVQWQIYPIKBCT-UHFFFAOYSA-N methoxy-phenyl-propan-2-yloxysilane Chemical compound CC(O[SiH](OC)C1=CC=CC=C1)C KDVQWQIYPIKBCT-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000001955 polymer synthesis method Methods 0.000 description 1
- 238000009715 pressure infiltration Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G77/04—Polysiloxanes
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- 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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- 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
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- 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
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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Abstract
The invention relates to siloxane-bridged-group ladder-shaped polysiloxane blocked by siloxane-bridged silane and a preparation method thereof. The invention provides siloxane bridging silane (namely bifunctional I-shaped silane) terminated siloxane bridging ladder-shaped polysiloxane and a preparation method thereof. The siloxane bridge-terminated trapezoidal polysiloxane with the following general formula is obtained by co-hydrolyzing a tetrafunctional I-shaped siloxane bridge-based siloxane monomer and a bifunctional I-shaped siloxane bridge-based silane end-capping agent, and forming a trapezoidal superstructure by virtue of the synergistic action of supermolecule weak bonds to regulate and control the polymerization and end-capping reaction of a hydrolysate. Compared with the common monofunctional end-capped siloxane bridge-based trapezoidal polysiloxane, the degree of polymerization and the end-capping completeness of the bifunctional I-shaped silane end-capped trapezoidal polysiloxane can be effectively controlled. The polymer has excellent heat resistance, good mechanical property and good compatibility with general organic polymers. And the raw materials used in the end-capping mode are simple and easy to obtain, the cost is low, and the method is suitable for industrialization.
Description
Technical Field
The invention relates to siloxane-bridged ladder-shaped polysiloxane, in particular to siloxane-bridged silane-terminated siloxane-bridged ladder-shaped polysiloxane and a preparation method thereof.
Background
Typically, ladder silicone polymers have a double-stranded ladder structure. Although the ladder-shaped main chain is broken by external action, statistically, the possibility that the upper and lower single chains of the same ladder support are broken simultaneously is very low. Therefore, compared with the common single-chain organic silicon polymer, the single-chain organic silicon polymer has more excellent performances in the aspects of heat resistance, radiation resistance, chemical resistance, mechanics and biological action.
The development of ladder organopolysiloxanes is divided into three stages depending on the structure of the bridge group: the first generation is an oxygen bridged ladder polysiloxane (i.e., ladder polysilsesquioxane, abbreviated as R-LPSQ, R represents a pendant group); the second generation is organic bridged ladder polysiloxane (English abbreviation R-OLPS, R stands for side group); the third generation is siloxane bridged ladder polysiloxane (abbreviated as R-SLPS in English, R represents a side group).
As early as 1960, previous soviet k.a.andrianov et al (izu.akad.nauk.s.s.s.r., Otdel khim.nauk,1960,1266) attempted to synthesize phenylbridge ladder polysiloxane (Ph-OLPS) and failed to obtain only random oligomers. In the same year, R-SLPS U.S. J.F.Brown et al (J.Am.chem.Soc.1960,82,6194) reported the synthesis of ladder-shaped polyphenylsilsesquioxane (Ph-LPSQ) using the "equilibrium thermal polycondensation" method. Great booming has ensued internationally and a large number of articles and patents have appeared concerning ladder-shaped polysilsesquioxanes of different side groups. However, in 1971 U.S. C.L.Frey et al disclaim the presence of the above ladder-shaped polyphenylsilsesquioxanes, it was noted that the polymerization reaction did not reach equilibrium in nature and the product was a partially ring-opened polycyclic cage (J.Am.chem.Soc.1971,93,4599). Since then, the European and American chemical core journal has no longer published articles on trapezoidal polysiloxanes. Since 1983, the ficus microcarpa group firstly synthesized oxygen-bridged ladder-shaped polysiloxane R-LPSQ (International patent WO 2010034161-A1; Angew. chem. int. Ed.2006,45,3112 and chem. Commun.2009,4079) and ladder-shaped polysiloxane R-OLPS of organic bridging group (Chinese patent CN 1280995A, U.S. Pat. No. 6423772B 1; J.Am. chem. Soc.2002,124,10482) respectively by adopting a supramolecular chemical method. Generally, the oxygen-bridged ladder-shaped polysilsesquioxane has better heat resistance, can be dissolved in a certain solvent, but has poor flexibility and limited application. And organic bridging ladderCompared with oxygen-bridge-based trapezoidal polysilsesquioxane, polysiloxane has improved flexibility, good compatibility with common organic polymers, and favorable improvement on the performance of the organic polymers, but the heat resistance of the polysiloxane is slightly inferior to that of the oxygen-bridge-based trapezoidal polysilsesquioxane. In 2014, this group disclosed siloxane bridge ladder polysiloxane homopolymer R-SLPS and its preparation method (Chinese patent CN 10404583B). The siloxane bridge group ladder-shaped polysiloxane has the advantages of the two ladder-shaped polysiloxanes, namely excellent heat resistance, good mechanical property and good compatibility with other organic macromolecules. These characteristics make it representative of a new generation of ladder polysiloxanes with excellent overall properties. However, there are currently problems, including: generally, the blocking agent used is a monofunctional silane (e.g., trimethylsiloxy, etc.), which limits its heat resistance; the end capping is not easy to complete; and the degree of polymerization is difficult to control; in addition, the blocking agent has a single structure and is expensive, which causes difficulties in practical application. The siloxane-bridged ladder-shaped polysiloxane has more excellent heat resistance compared with monofunctional silane-terminated siloxane-bridged ladder-shaped polysiloxane, for example, the hydroxyl-terminated ladder-shaped polymer 4HO-blocked Ph-SLPS does not change color or crosslink at 400 ℃ for 15h, which becomes the highest heat resistance data of common polysiloxane reported by the literature so far, and the corresponding monofunctional silane (such as diphenyl methyl silyl) terminated siloxane-bridged ladder-shaped polysiloxane MePh2SiO-blocked Ph-SLPS also shows better performance at 400 ℃ for 15h without cross-linking and discoloration. And the corresponding diphenylsiloxane bridging silane-terminated siloxane bridging ladder polysiloxane Ph2the-I-Ph-SLPS shows better performance, and does not crosslink and discolor at 400 ℃ for 24 hours. And the adopted high-boiling point bifunctional silane end-capping agent is not easy to escape under the high vacuum condition, so that the end capping is more complete. The polymerization degree of the trapezoidal polymer can be effectively controlled by adjusting the gram-molecule ratio of the bifunctional I-shaped end-capping agent to the tetrafunctional I-shaped monomer. The double-official-shaped end-capping agent has the advantages of easily obtained raw materials, expanded diversity of end groups, simplified operation process, reduced cost and more convenience for industrialization.
Disclosure of Invention
It is an object of the present invention to provide a siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxane, wherein the siloxane-bridged ladder polysiloxane has a molecular structure of the following formula (1):
wherein:
m is an integer of 1 to 10,
n is an integer of 1 to 1000,
A1、A2、A3、A4、A5、A6each independently selected from hydrogen, substituted or unsubstituted straight, branched or cyclic C1-25Alkyl, substituted or unsubstituted straight, branched or cyclic C2-25Alkenyl, substituted or unsubstituted C5-25An aryl group, a heteroaryl group,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10each independently selected from hydrogen, hydroxy, substituted or unsubstituted straight, branched or cyclic C1-25Alkyl, substituted or unsubstituted straight, branched or cyclic C2-25Alkenyl, substituted or unsubstituted C5-25Aryl, substituted or unsubstituted, straight, branched or cyclic C1-25Alkoxy, substituted or unsubstituted C5-25An aryloxy group which is a group having a lower alkoxy group,
when the above group has a substituent, the substituent is at least one selected from the group consisting of: straight, branched or cyclic C1-25Alkyl, straight, branched or cyclic C2-25Alkenyl radical, C5-25An aryl group, a group containing at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom, a halogen atom,
each of the above alkyl group, alkoxy group, alkenyl group, aryl group and aryloxy group may have at least one hetero atom selected from the group consisting of O, S, P, N as a chain constituting atom or a ring constituting atom in a chain or a ring.
Another object of the present invention is to provide a process for preparing a siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxane having the structure of formula (1) as described above.
The preparation method is characterized in that a tetrafunctional I-shaped siloxane bridging group siloxane monomer and a bifunctional I-shaped siloxane bridging group silane end-capping agent are subjected to cohydrolysis, and a trapezoidal superstructure is formed by virtue of the synergistic action of supermolecule weak bonds to regulate and control polymerization and end-capping reaction, so that the siloxane bridging group silane end-capped siloxane bridging group trapezoidal polysiloxane with the structure shown in the formula (1) is obtained.
As the I-shaped monomer used for polymerization is a tetrafunctional compound, branching and crosslinking are easy to occur under the hydrolysis and condensation conditions, and insoluble and infusible gel is generated. For this reason, unlike conventional polymer synthesis methods, the synthesis of siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxanes according to the present invention involves the use of supramolecular chemistry to regulate the polymerization process. Namely, the monomer forms a trapezoidal superstructure through the synergistic action of supermolecule weak bonds (including pi-pi superposition, interaction of an electron donor and an acceptor, static electricity, hydrophilic and hydrophobic, hydrogen bonds and the like) in the hydrolysis process to regulate and control polymerization reaction, and the occurrence of branching and crosslinking is inhibited, so that the trapezoidal polymer with a regular structure is obtained; meanwhile, a trapezoidal superstructure is formed by means of the supermolecule weak bond synergistic action between the tetrafunctional end group polymer and the double-official-shaped silane end-capping agent molecules, so that the end-capping reaction is smoothly carried out. Considering that the synergistic effect of the supermolecule weak bond formed in the reaction process is obviously influenced by the reaction temperature and the polarity of the solvent, a proper reaction temperature (including hydrolysis, condensation and blocking reaction early-stage temperature is lower (-50 ℃ to 50 ℃) so as to ensure the stability of the trapezoidal superstructure constructed by the supermolecule weak interaction, and a proper temperature (100 ℃) and a reaction solvent with proper polarity and weak interaction groups are required for blocking completely in the blocking reaction later stage so as to obtain the trapezoidal polymer with a regular structure and complete blocking.
Specifically, the present application provides the following inventions
In a first aspect of the present invention, there is provided a siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxane having the following molecular structure of formula (1):
wherein:
m is an integer of 1 to 10,
n is an integer of 1 to 1000,
A1、A2、A3、A4、A5、A6each independently selected from hydrogen, substituted or unsubstituted straight, branched or cyclic C1-25Alkyl, substituted or unsubstituted straight, branched or cyclic C2-25Alkenyl, substituted or unsubstituted C5-25An aryl group, a heteroaryl group,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10each independently selected from hydrogen, hydroxy, substituted or unsubstituted straight, branched or cyclic C1-25Alkyl, substituted or unsubstituted straight, branched or cyclic C2-25Alkenyl, substituted or unsubstituted C5-25Aryl, substituted or unsubstituted, straight, branched or cyclic C1-25Alkoxy, substituted or unsubstituted C5-25An aryloxy group which is a group having a lower alkoxy group,
when the above group has a substituent, the substituent is at least one selected from the group consisting of: straight, branched or cyclic C1-25Alkyl, straight, branched or cyclic C2-25Alkenyl radical, C5-25An aryl group, a group containing at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom, a halogen atom,
each of the above alkyl group, alkoxy group, alkenyl group, aryl group and aryloxy group may have at least one hetero atom selected from the group consisting of O, S, P, N as a chain constituting atom or a ring constituting atom in a chain or a ring.
In another preferred embodiment, the group containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom is selected from the group consisting of a hydroxyl group, a glycidoxy group, C5-25Epoxycycloalkyl, acryloxy, C1-25Alkyl-substituted acryloxy, mercapto, amino-straight, branched or cyclic C1-25Alkyl radical, C6-25Arylamino, cyano, ureido, phosphino.
In another preferred embodiment, R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、A1、A2、A3、A4、A5、A6Each independently selected from the group consisting of hydrogen, hydroxy, methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, tert-butyl, N-hexyl, cyclohexyl, N-octyl, N-decyl, N-dodecyl, N-hexadecyl, N-octadecyl, N-docosyl, vinyl, allyl, phenyl, methylphenyl, chlorophenyl, p-vinylphenyl, 3- (2, 3-epoxypropoxy) propyl, 2- (3, 4-epoxycyclohexyl) ethyl, acryloxypropyl, 3-methacryloxypropyl, mercaptopropyl, aminopropyl, 3- (2-aminoethyl) -aminopropyl, 4-amino-3, 3-dimethylbutyl, N-N-butyl-3-aminopropyl, 2-cyanoethyl, 3-cyanopropyl, 3,3, 3-trifluoropropyl group, 1H,2H, 2H-perfluorooctyl group, 1H,2H, 2H-perfluorodecyl group, chloropropyl group, ureidopropyl group, methoxy group and ethoxy group.
The invention provides a preparation method of siloxane bridge-terminated ladder-shaped polysiloxane according to the structure of the formula (1), which is characterized in that a tetrafunctional I-shaped siloxane bridge-shaped siloxane monomer and a bifunctional I-shaped siloxane bridge-shaped silane end-capping agent are subjected to cohydrolysis, and a ladder-shaped superstructure is formed by virtue of the synergistic action of supermolecular weak bonds to regulate and control polymerization and end-capping reactions, so that the siloxane bridge-terminated ladder-shaped polysiloxane with the structure of the formula (1) is obtained.
In another preferred embodiment, the method for preparing the siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxane comprises the following steps:
adding silane with structural formulas (2), (3) and (4), organic solvent, water and catalyst into a reactor to carry out hydrolysis and condensation reaction, and continuously or discontinuously vacuumizing to remove condensation byproducts; and then separating and purifying the product obtained by the reaction to obtain the siloxane-bridged group ladder-shaped polysiloxane with the structure of the formula (1) and terminated by siloxane-bridged group silane.
The tetrafunctional I-shaped siloxane bridging group siloxane monomer (2) is represented by a structural formula (2)
Wherein,
m、R1、R2、A1、A2each having the same meaning as described in claim 1;
x is selected from OH, halogen and C1-25Alkoxy or C1-25One of acyloxy groups;
the bifunctional I-shaped siloxane bridging silane end-capping agent (3) is represented by a structural formula (3)
Wherein,
m、R3、R4、R5、R6、A3、A4each having the same meaning as described in claim 1;
x is selected from OH, halogen and C1-25Alkoxy or C1-25One of acyloxy groups;
the bifunctional I-shaped siloxane bridging silane end-capping agent (4) is represented by a structural formula (4)
Wherein,
m、R7、R8、R9、R10、A5、A6are each as defined in claim 1;
x is selected from OH, halogen and C1-25Alkoxy radicalOr C1-25One of acyloxy groups;
in another preferred embodiment, the tetrafunctional I-shaped siloxane bridging group siloxane monomer of formula (2) is prepared by condensing a trifunctional silane coupling agent with a silicon diol in the presence of a catalyst,
the trifunctional silane coupling agent is represented by the formula-RSiX3It is shown that,
wherein R ═ R1,R2(ii) a X is halogen, C1-25Alkoxy radical, C1-25And (4) acyloxy.
In another preferred embodiment, the bifunctional I-shaped siloxane bridging silane end-capping agent of formula (3) is prepared by condensing a bifunctional silane coupling agent with a silicon diol in the presence of a catalyst,
the bifunctional silane coupling agent is represented by the formula R' SiX2It is shown that,
wherein R', R ═ R3And R5Combination, R4And R6Combining; x is halogen, C1-25Alkoxy radical, C1-25And (4) acyloxy.
The bifunctional I-shaped siloxane bridging group silane end-capping agent of formula (4) is prepared by condensing a bifunctional silane coupling agent and silicon glycol in the presence of a catalyst,
the bifunctional silane coupling agent is represented by the formula R' SiX2It is shown that,
wherein R', R ═ R7And R9Combination, R8And R10Combining; x is halogen, C1-25Alkoxy radical, C1-25And (4) acyloxy.
In a further preferred embodiment of the method,
the reaction temperature is-50 ℃ to 150 ℃, usually-45 ℃ to 100 ℃. Wherein the hydrolysis and condensation reaction temperature is-50 ℃ to 50 ℃; the end-capping reaction temperature is-50 ℃ to 50 ℃ in the early stage, and the end-capping complete reaction temperature can be increased to 100 ℃ in the later stage.
In another preferred embodiment, the organic solvent is selected from: one or more of alkanes, substituted alkanes, alcohols, ethers, ketones, esters, amides, nitriles, pyrrolidones, sulfoxides.
In another preferred embodiment, the organic solvent is selected from: one or more of N-hexane, cyclohexane, dichloroethane, trichloromethane, tetrachloroethane, methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1, 4-dioxane, acetone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, acetonitrile, N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO).
In another preferred embodiment, the reaction time is 30 minutes to 120 hours.
In another preferred embodiment, the number of moles of water added to said silane of formula (2) is 0.001 to 50 times the number of moles of silane of formula (2).
In another preferred embodiment, the silane of formula (3) or (4) is added to the silane of formula (2) in a molar amount of 0.001 to 20 times the molar amount of the silane of formula (2).
In another preferred embodiment, the catalyst is added to the silane of formula (2) in a molar amount 0 to 10 times the molar amount of the silane of formula (2).
In another preferred embodiment, the solvent is added to the silane of formula (2) in a molar amount of 1-1000% based on the weight of the silane of formula (2), (3) or (4).
In another preferred embodiment, the addition of the silanes of the formulae (3) and (4) in the dropwise or "one-pot" process is continued or indirect at-50 ℃ to 150 ℃ for a reaction time of 0 min to 120 h under vacuum.
In another preferred embodiment, the yield of the siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxane with the structure of the formula (1) is 70-100%.
In another preferred embodiment, the catalyst is one or more selected from acid, oxide and hydroxide, ammonia or amine, transition metal compound and ion exchange resin, and organic amine and oxide and hydroxide catalysts are preferred for obtaining the ladder-shaped polymer with regular structure and complete end capping.
In another preferred example, the acid catalyst is one or more of inorganic acids and organic acids.
In another preferred embodiment, the oxide is one or more selected from metal oxides.
In another preferred embodiment, the hydroxide is one or more selected from tetramethylammonium hydroxide, tetrabutyl phosphorus hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide and barium hydroxide.
In another preferred example, the transition metal compound is one or more selected from organic tin and titanate.
In another preferred example, the amine is one or more selected from tertiary amines.
In another preferred embodiment, the ion exchange resin is one or more selected from quaternary ammonium type ion exchange resin with styrene divinylbenzene copolymer as matrix, sulfonic acid type ion exchange resin with styrene divinylbenzene copolymer as matrix, carboxylic acid type ion exchange resin with styrene divinylbenzene copolymer as matrix, and carboxylic acid type ion exchange resin with polyacrylic acid as matrix.
In another preferred example, the acid catalyst is one or more of hydrochloric acid, sulfuric acid, formic acid and acetic acid.
In another preferred example, the oxide is one or more selected from calcium oxide and magnesium oxide.
In another preferred embodiment, the transition metal compound is one or more selected from dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide and butyl titanate.
In another preferred embodiment, the amine is one or more selected from the group consisting of ammonia, n-butylamine, t-butylamine, dimethylamine, diethylamine, diisopropylamine, ethylenediamine, tetramethylammonium hydroxide, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] -5-nonene, triethylamine, pyridine and triethanolamine.
The invention has the beneficial effects that:
a) the siloxane bridging group ladder-shaped polysiloxane blocked by siloxane bridging silane can effectively control the polymerization degree by adjusting the using amount of a bifunctional I-shaped blocking agent, and can continuously remove by-products under high vacuum so as to enable blocking reaction to be more complete. Compared with a monofunctional end-capping mode, the method has better heat resistance, chemical stability and mechanical property.
b) The siloxane bridge-terminated ladder-shaped polysiloxane has the advantages that the bridge group, the end group and the side group are all organic groups, the compatibility with general polymers is good, the problems of uncontrollable polymerization degree, single structure of the end-capped functional group, high price and incomplete end capping of the existing monofunctional siloxane end-capped ladder-shaped polysiloxane are solved due to the diversity of end-capping agents and the uniqueness of a preparation method, and the optical activity, the light transmittance, the adhesion, the air tightness, the strength and the like are adjusted by changing the bridge group, the side group, the end group and the polymerization degree, so that the application range is wider.
c) The siloxane-bridged-group trapezoidal polysiloxane terminated by siloxane-bridged-group silane has excellent high temperature resistance, high weather resistance, high radiation resistance and good optical and mechanical properties. The high-temperature-resistant silicon rubber can be widely applied to the high-technology field as novel materials such as high-temperature-resistant silicon rubber, high-heat-resistant and high-weather-resistant coatings, photocuring coatings, light-emitting diodes and electronic packaging materials, high-temperature-resistant and high-vacuum diffusion pump oil, high-temperature-resistant lubricants, special coupling agents and the like.
Drawings
FIG. 1 shows the product obtained in example 1 of the present invention29Si-NMR spectrum.
FIG. 2 is an FTIR spectrum of the product obtained in example 1 of the present invention.
FIG. 3 shows the product obtained in example 3 of the present invention29Si-NMR spectrum.
FIG. 4 is an FTIR spectrum of the product obtained in example 5 of the present invention.
FIG. 5 shows the product obtained in example 5 of the present invention29Si-NMR spectrum.
FIG. 6 is a DSC spectrum of the product obtained in example 5 of the present invention.
FIG. 7 is a TGA profile of the product obtained in example 5 of the present invention.
FIG. 8 is a TGA profile of the product obtained in example 6 of the present invention.
FIG. 9 is a DSC spectrum of the product obtained in example 6 of the present invention.
FIG. 10 is a TGA profile of a comparative product used in example 6 of the present invention.
FIG. 11 is a DSC spectrum of a comparative product used in example 6 of the present invention.
Detailed Description
The following describes specific embodiments of the present application. However, these embodiments are merely examples, and are not intended to limit the scope of the invention of the present application.
The siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxane of the present embodiment has a molecular structure represented by the following formula (1):
wherein:
m is an integer of 1 to 10,
n is an integer of 1 to 1000,
A1、A2、A3、A4、A5、A6each independently selected from hydrogen, substituted or unsubstituted straight, branched or cyclic C1-25Alkyl, substituted or unsubstituted straight, branched or cyclic C2-25Alkenyl, substituted or unsubstituted C5-25An aryl group, a heteroaryl group,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10each independently selected from hydrogen, hydroxy, substituted or unsubstituted straight, branched or cyclic C1-25Alkyl, substituted or unsubstituted straight, branched or cyclic C2-25Alkenyl, substituted or unsubstituted C5-25Aryl, substituted or unsubstituted, straight, branched or cyclic C1-25Alkoxy, substituted or unsubstituted C5-25An aryloxy group which is a group having a lower alkoxy group,
when the above group has a substituent, the substituent is at least one selected from the group consisting of: straight, branched or cyclic C1-25Alkyl, straight, branched or cyclic C2-25Alkenyl radical, C5-25An aryl group, a group containing at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom, a halogen atom,
each of the above alkyl group, alkoxy group, alkenyl group, aryl group and aryloxy group may have at least one hetero atom selected from the group consisting of O, S, P, N as a chain constituting atom or a ring constituting atom in a chain or a ring.
In the present invention, C1-25The alkyl group represents an alkyl group having 1 to 25 carbon atoms. Other similar terms are also the same.
Straight, branched or cyclic C1-25Alkyl groups may be listed but not limited to straight chain C1-25Alkyl, branched C1-25Alkyl, cyclic C3-25Alkyl, preferably straight-chain C1-25An alkyl group. The number of carbon atoms of the alkyl group may be 1 to 22, 1 to 20, 1 to 18, 1 to 16, 1 to 12, 1 to 10, 1 to 6, 1 to 4, preferably 1 to 6. Specific examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cycloeicosyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cyclooctadecyl, cyclodocosyl, cycloeicosyl, and the like, Cycloeicosyl, cyclotetracosyl, and cyclopentacalkyl.
Straight, branched or cyclic C2-25Alkenyl groups may be listed but are not limited to straight chain C2-25Alkenyl, branched C2-25Alkenyl, cyclic C3-25Alkenyl, preferably straight-chain C2-25Alkenyl radical. The number of carbon atoms of the alkenyl group may be 2 to 22, 2 to 20, 2 to 18, 2 to 16, 2 to 12, 2 to 10, 2 to 6, 2 to 4, preferably 2 to 3. Specific examples thereof include: vinyl, propenyl, allyl.
C5-25Aryl can be enumerated by, but is not limited to, C5～20Aryl radical, C5-18Aryl radical, C5-14And (4) an aryl group. Specific examples thereof include pyridyl, phenyl and naphthyl.
Straight, branched or cyclic C1-25Alkoxy being straight, branched or cyclic C1-25A group in which an alkyl group is bonded to an oxygen (O) atom, wherein C is a linear, branched or cyclic group1-25Examples of alkyl groups are as described above.
C5-25Aryloxy is C5-25A group formed by bonding an aryl group to an oxygen (O) atom, wherein C5-25Examples of aryl groups are as described above.
The alkyl group, alkoxy group, alkenyl group, aryl group and aryloxy group may each have at least one hetero atom selected from the group consisting of O, S, P, N as a chain-constituting atom or a ring-constituting atom in a chain or a ring, and thus may be a heteroalkyl group, a heteroalkoxy group, a heteroalkenyl group, a heteroaryl group or a heteroaryloxy group.
Examples of the group containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom include, but are not limited to, a hydroxyl group, a carbonyl group, an oxo group (═ O), and a linear, branched or cyclic C1-25Alkoxy radical, C5-25Aryloxy, glycidoxy, C5-25Epoxycycloalkyl, acryloxy, straight, branched or cyclic C1-25Alkyl-substituted acryloxy, mercapto, straight, branched or cyclic C1-25Alkylthio, sulfo, nitro, amino-straight, branched or cyclic C1-25Alkyl radical, C5-25Arylamino, cyano, ureido, phosphino, straight, branched or cyclic C1-25An alkyl-substituted phosphino group.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferred.
The method for preparing the siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane of the present embodiment comprises: the tetrafunctional I-shaped siloxane bridging siloxane monomer and the bifunctional I-shaped siloxane bridging silane end-capping agent are subjected to cohydrolysis, and a trapezoidal superstructure is formed by virtue of the synergistic action of supermolecule weak bonds to regulate and control polymerization and end-capping reactions, so that the siloxane bridging silane end-capped trapezoidal polysiloxane with the structure shown in the formula (1) is obtained.
Preferably, the method of preparing the siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxane of the present embodiment comprises the steps of: the siloxane-bridged-group ladder-shaped polysiloxane blocked by siloxane-bridged silane is prepared by co-hydrolyzing silane (shown in structural formulas (2), (3) and (4) (namely a tetrafunctional I-shaped siloxane-bridged-group siloxane monomer and a bifunctional I-shaped siloxane-bridged-group silane blocking agent) in the presence of a solvent, a catalyst and water, and forming a ladder-shaped superstructure by virtue of supermolecular weak bond interaction (including pi-pi superposition, interaction of an electron donor and an acceptor, electrostatic interaction, hydrophilic interaction, hydrophobic interaction, hydrogen bond and the like) to regulate and control polymerization and blocking reaction of a hydrolysate. The preparation method comprises the following steps:
adding silane with the structural formulas (2), (3) and (4), a solvent, water and a catalyst into a reactor in a dropwise adding or one-pot boiling mode to perform hydrolysis and condensation reaction, performing intermittent or continuous vacuum pumping reaction, and performing separation, purification and other treatments on a product obtained by the reaction to obtain the siloxane-bridged-group ladder-shaped polysiloxane blocked by siloxane-bridged-group silane with the structure of the formula (1), wherein the yield is 70-100%.
Said tetrafunctional i-shaped siloxane bridging siloxane monomer (2) is represented by structural formula (2):
wherein,
m、R1、R2、A1、A2each has the same meaning as defined above;
x is selected from OH, halogen and C1-25Alkoxy or C1-25One of acyloxy groups;
the bifunctional i-shaped siloxane bridging silane end-capping agent (3) is represented by structural formula (3):
wherein,
m、R3、R4、R5、R6、A3、A4each has the same meaning as defined above;
x is selected from OH, halogen and C1-25Alkoxy or C1-25One of acyloxy groups;
the bifunctional i-shaped siloxane bridging silane end-capping agent (4) is represented by structural formula (4):
wherein,
m、R7、R8、R9、R10、A5、A6each has the same meaning as defined above;
x is selected from OH, halogen and C1-25Alkoxy or C1-25One of acyloxy groups;
the above-mentioned tetrafunctional I-shaped siloxane-bridged siloxane monomer (2) is preferably prepared from a trifunctional silane coupling agent-RSiX3(R＝R1,R2(ii) a X is halogen, C1-25Alkoxy radical, C1-25Acyloxy and the like; such as methyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, propyltrimethoxysilane methacrylate, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane and the like, with a silicon diol (such as diphenylsilanediol, di-t-butylsilanediol and the like) in the presence of a catalyst, including dealcoholization, dehydration, dehydrohalogenation, deacidification or deesterification.
The bifunctional I-shaped siloxane bridging silane blocking agents (3) and (4) are preferably prepared from bifunctional silane coupling agents-R' SiX2(R’R”＝R3And R5Combination, R4And R6Combination or R7And R9Combination, R8And R10Combining; x ═ halogen, alkoxy, acyloxy, and the like) and silicon glycol (a)3A4Si(OH)2,A5A6Si(OH)2Specific examples thereof include diphenylsilanediol, methylphenylsilicediol, di-t-butylsilanediol and the like) in the presence of a catalyst (including dealcoholization, dehydration, dehydrohalogenation, deacidification or deesterification). The R is3-R10、A3、A4、A5、A6Respectively as described above, said R3、R5Which may be the same or different, said R4、R6Which may be the same or different, said R7、R9Which may be the same or different, said R8、R10Which may be the same or different, said A3、A4Which may be the same or different, said A5、A6Which may be the same or different, said R3And R5Combination, R4And R6The combination may be the same or different, and R is7And R9Combination, R8And R10The combinations may be the same or different.
Preferably, R in the formula (1), the formula (2), the formula (3) and the formula (4)1、R2、R3、R4、R5、R6、R7、R8、R9、R10、A1、A2、A3、A4、A5、A6Each independently selected from hydrogen, hydroxyl, and C1-25 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl, and aryl groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, octyl, n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl, n-docosyl, vinyl, allyl, phenyl, methylphenyl, chlorophenyl, p-vinylphenyl, 3- (2, 3-epoxypropoxy) propyl, 2- (3, 4-epoxycyclohexyl) ethyl, acryloxypropyl, 3-methacryloxypropyl, mercaptopropyl, aminopropyl, 3- (2-aminoethyl) -aminopropyl, 4-amino-3, 3-one of dimethylbutyl, N-butyl-3-aminopropyl, 2-cyanoethyl, 3-cyanopropyl, 3,3, 3-trifluoropropyl, 1H, 2H-perfluorooctyl, 1H, 2H-perfluorodecyl, chloropropyl, ureidopropyl, methoxy and ethoxy.
The reaction temperature is not particularly limited, and is usually from-50 ℃ to 150 ℃, for example from-45 ℃ to 100 ℃. Wherein the hydrolysis and condensation reaction temperature is-50 ℃ to 50 ℃; the end-capping reaction temperature is-50 ℃ to 50 ℃ in the early stage, and the end-capping complete reaction temperature can be increased to 100 ℃ in the later stage.
The reaction time is not particularly limited, and is usually 30 minutes to 120 hours, for example, 1 hour to 80 hours.
The amount of water added to the silane of the formula (2) is not particularly limited, and generally the number of moles of water is 0.001 to 50 times, for example, 0.01 to 30 times the number of moles of the silane of the formula (2).
The amount of the silane of the formula (3) or (4) added to the silane of the formula (2) is not particularly limited, and usually the respective moles of the silane of the formula (3) or (4) are from 0.001 to 20 times, for example from 0.01 to 10 times, the moles of the silane of the formula (2).
The amount of the catalyst added to the silane of the formula (2) is not particularly limited, and usually the number of moles of the catalyst is 0 to 10 times, for example, 0.01 to 5 times the number of moles of the silane of the formula (2).
The amount of the solvent added to the silane of the formula (2) is not particularly limited, and usually the weight of the solvent is 1 to 1000%, for example, 2 to 500% of the total weight of the silanes of the formulae (2), (3) and (4).
Preferably, the addition of the silanes of the formulae (3) and (4) dropwise or in a "one-pot" is followed continuously or indirectly by a reaction under vacuum at from-50 ℃ to 150 ℃ for from 0 minute to 120 hours, for example from 1 minute to 72 hours.
The organic solvent is preferably selected from: alkanes (such as N-hexane, cyclohexane, etc.), substituted alkanes (such as chloroform, tetrachloroethane, etc.), alcohols (such as methanol, ethanol, etc.), ethers (such as diethylene glycol dimethyl ether, tetrahydrofuran, 1, 4-dioxane, etc.), ketones (such as acetone, cyclohexanone, etc.), esters (such as ethyl acetate, etc.), amides (such as dimethylacetamide, etc.), nitriles (such as acetonitrile, etc.), pyrrolidones (such as N-methylpyrrolidone (NMP)), sulfoxides (such as dimethyl sulfoxide (DMSO), etc.). In the reaction process, the supermolecule weak bond synergistic effect between the tetrafunctional end group polymer and the double-official-style silane end capping agent molecules is significantly influenced by the polarity of the solvent, so that a reaction solvent with proper polarity and weak interaction groups is required to be selected to obtain the ladder-shaped polymer with a regular structure and complete end capping, and the organic solvent is preferably selected from the following groups: one or more of N-hexane, cyclohexane, dichloroethane, trichloromethane, tetrachloroethane, methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1, 4-dioxane, acetone, cyclohexanone, methyl isobutyl ketone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, acetonitrile, N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO).
The catalyst is preferably one or more selected from acid, oxide and hydroxide, ammonia or amine, transition metal compound and ion exchange resin, and in order to obtain the ladder-shaped polymer with regular structure and complete end capping, the catalyst is preferably amine, oxide and hydroxide catalyst. Further silane coupling agents which may be selected for the preparation of the silanes of the formulae (2), (3) and (4) are condensed in the presence of the catalysts mentioned above.
The acid catalyst is preferably one or more selected from inorganic acids (such as hydrochloric acid, sulfuric acid and the like) and organic acids (such as formic acid, acetic acid and the like);
the oxide is preferably one or more selected from metal oxides (such as calcium oxide, magnesium oxide and the like);
the hydroxide is preferably one or more selected from tetramethyl ammonium hydroxide, tetrabutyl phosphorus hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide and barium hydroxide;
the transition metal compound is preferably one or more selected from organic tin (such as dibutyl tin dilaurate, dibutyl tin diacetate and the like) and titanate (such as butyl titanate and the like);
the ammonia or amine is preferably one or more selected from ammonia gas, n-butylamine, tert-butylamine, dimethylamine, diethylamine, diisopropylamine, ethylenediamine, tetramethylammonium hydroxide, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] -5-nonene, triethylamine, pyridine and triethanolamine;
the ion exchange resin is preferably one or more selected from quaternary ammonium ion exchange resin taking styrene divinylbenzene copolymer as a matrix, sulfonic acid ion exchange resin taking styrene divinylbenzene copolymer as a matrix, carboxylic acid ion exchange resin taking styrene divinylbenzene copolymer as a matrix and carboxylic acid ion exchange resin taking polyacrylic acid as a matrix.
The siloxane bridged group ladder-shaped polysiloxane terminated by siloxane bridged group silane can be changed from colorless transparent liquid to solid according to the size of molecular weight and different appearances of the end group side bridged group, and has excellent light transmittance, excellent temperature resistance and flexibility. The compound has good solubility in solvents such as tetrahydrofuran, 1, 4-dioxane, toluene, N-methylpyrrolidone, acetone, DMA and the like, the composition structure is proved by tests such as nuclear magnetic hydrogen spectrum, nuclear magnetic silicon spectrum, infrared spectrum, heat scanning calorimetry (DSC) and the like, the average polymerization degree can be calculated by nuclear magnetic silicon spectrum, vapor pressure infiltration (VPO) and the like, and the viscosity change caused by the difference of polymerization degrees can be reflected from another angle by testing the viscosity value under high-temperature melting.
Glass transition temperature (T)g) The measurement is carried out by a scanning calorimetry (DSC), the testing condition of the DSC is that the temperature is increased from the lowest temperature to be tested to the highest temperature to be tested at 20 ℃/min, then the temperature is rapidly cooled from the highest temperature to the lowest temperature, and the second temperature rise detection is carried out at 10 ℃/min.
The refractive index is measured by an Abbe refractometer, and the test condition of the refractive index is that the film is coated for measurement under the constant temperature condition of 298K.
The viscosity was measured by melting the sample at high temperature with a high-temperature cone-plate viscometer and selecting an appropriate rotation speed.
The thermal decomposition temperature is measured by a thermogravimetric analyzer (TGA), and the test condition of the TGA is that the temperature is raised from 30 ℃ to 900 ℃ at 20 ℃/min under an air atmosphere; or heating from 30 deg.C to 600 deg.C at 20 deg.C/min under nitrogen atmosphere, and heating from 600 deg.C to 900 deg.C at 20 deg.C/min under air atmosphere.
The present embodiment will be described in more detail below with reference to examples. However, the present invention is not limited to these examples.
For simplicity, the following I-shaped silane-terminated siloxane bridging polysiloxanes are abbreviated as R' -I-R-SLPS, wherein: r is a side group of polysiloxane R-SLPS. I-represents the end capping of I-shaped silane; r' represents the two end groups of the I-shaped silane.
Example 1: ph2Synthesis of-I-Ph-SLPS
The siloxane-bridged silane-terminated ladder polysiloxanes were prepared from phenyltrimethoxysilane, diphenyldimethoxysilane and diphenylsilanediol.
Placing 39.6 g of phenyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.01mol) and 15 g of ethyl acetate in a three-neck flask provided with a mechanical stirrer, a constant pressure dropping funnel and a reflux condenser under the protection of dry nitrogen, uniformly stirring at room temperature, adding 0.02 g of triethanolamine at 0 ℃, and reacting for 8 hours to obtain an intermediate 1; simultaneously, adding 41.9 g of diphenyldimethoxysilane (0.17mol), 10 g of ethyl acetate and 18.6 g of diphenylsilanediol (0.09mol) into another three-neck flask which is provided with a mechanical stirring, a constant pressure dropping funnel and a reflux condenser and is protected by dry nitrogen, uniformly stirring, adding 0.04 g of triethanolamine at 0 ℃ for reaction for 10 hours to obtain an intermediate 2, completely adding the intermediate 2 into the intermediate 1, adding 12.6 g (0.70mol) of water, reacting for 5 hours at-10 ℃, heating to 0 ℃ and continuing to react for 10 hours; then neutralizing the obtained mixture with hydrochloric acid, adding 50mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with the structure of formula (1), wherein R is1-R10Is phenyl, A1-A6For phenyl, m ═ 1, n ═ 14, and the yield obtained was 95%.
The resulting siloxane bridging silane end-capped siloxane bridging ladderThe polysiloxane was a colorless transparent solid, the average value of the degree of polymerization n was 14, the refractive index was 1.59(25 ℃), the glass transition temperature was 48.51 ℃, the viscosity was 133 poise (poise) at 230 ℃ and 800 rpm. The air thermal oxidation resistance is respectively as follows: the hydroxyl-terminated ladder-shaped polymer 4HO-blocked Ph-SLPS does not discolor or crosslink at 400 ℃ for 15 h; while the corresponding monofunctional silane (e.g. diphenylmethylsilyl) end-capped siloxane-bridged ladder polysiloxane MePh2SiO-I-blocked Ph-SLPS does not crosslink and change color at 400 ℃ for 15 h. And the corresponding diphenylsiloxane bridging silane-terminated siloxane bridging ladder polysiloxane Ph2the-I-Ph-SLPS shows better performance, and does not crosslink and discolor at 400 ℃ for 24 hours.1H NMR(400MHz,CDCl3,298K):δ7.14-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-79.16,-43.46ppm。
Example 2: PhMe-I-Ph-SLPS Synthesis
The siloxane-bridged silane-terminated ladder polysiloxanes were prepared from phenyltrimethoxysilane, methylphenyldimethoxysilane and diphenylsilanediol.
Placing 39.6 g of phenyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.10mol) and 10 g of N, N-dimethylacetamide into a three-neck flask provided with a mechanical stirrer, a constant-pressure dropping funnel and a reflux condenser under the protection of dry nitrogen, uniformly stirring at room temperature, adding 0.10 g of liquid ammonia at-5 ℃, and reacting for 12 hours to obtain an intermediate 1; simultaneously, 3.65 g of methyl phenyl dimethoxy silane (0.02mol), 10 g of N, N-dimethylacetamide and 2.16 g of diphenyl silanediol (0.01mol) are added into another three-neck flask which is provided with a dry nitrogen protection device and is provided with a mechanical stirring device, a constant pressure dropping funnel and a reflux condenser, and are uniformly stirred, 0.02 g of liquid ammonia is added at the temperature of 0 ℃ to react for 18 hours to obtain an intermediate 2, the intermediate 2 is completely added into the intermediate 1, 9.00 g (0.50mol) of water is added, and the reaction is carried out for 15 hours at the temperature of 0 ℃; then neutralizing the obtained mixture with hydrochloric acid, adding 20mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with the structure of formula (1), wherein R is1＝R2＝R3＝R4＝R7＝R8Is phenyl，R5＝R6＝R9＝R10Is methyl, A1-A6For phenyl, m ═ 1, n ═ 80, and the yield obtained was 92%.
The obtained siloxane bridging silane end-capped siloxane bridging trapezoidal polysiloxane is colorless transparent solid, the average value of the polymerization degree n is 80, the refractive index is 1.57(25 ℃), the glass transition temperature is 39.45 ℃, 230 ℃, and the viscosity is 2430 poise (poise) at the rotating speed of 50 rpm. The air thermal oxidation resistance is respectively as follows: the hydroxyl-terminated ladder-shaped polymer 4HO-blocked Ph-SLPS does not discolor or crosslink at 400 ℃ for 15 h; while the corresponding monofunctional silane (e.g. diphenylmethylsilyl) end-capped siloxane-bridged ladder polysiloxane MePh2SiO-I-blocked Ph-SLPS does not crosslink and change color at 400 ℃ for 15 h. The corresponding methyl phenyl siloxane bridging group silane end-blocked siloxane bridging group ladder-shaped polysiloxane PhMe-I-Ph-SLPS shows better performance and does not crosslink and discolor at 400 ℃ for 20 hours.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.11,7.14-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-80.02,-43.96,-27.23ppm。
Example 3: ph2-I-Me-SLPS Synthesis
The siloxane-bridged silane-terminated ladder polysiloxanes were prepared from methyltrimethoxysilane, diphenyldimethoxysilane and diphenylsilanediol.
Under the protection of dry nitrogen, placing 27.2 g of methyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.10mol) and 20 g of chloroform in a three-neck flask provided with a mechanical stirring device, a constant pressure dropping funnel and a reflux condenser, stirring uniformly at room temperature, adding 0.08 g of tetrabutylphosphine oxide at the temperature of-10 ℃, and reacting for 8 hours to obtain an intermediate 1; meanwhile, 48.9 g of diphenyldimethoxysilane (0.20mol), 40 g of trichloromethane and 21.6 g of diphenylsilanediol (0.10mol) are added into another three-neck flask which is protected by dry nitrogen and is provided with a mechanical stirrer, a constant pressure dropping funnel and a reflux condenser, and are uniformly stirred, 0.3 g of tetrabutylphosphine oxide is added at the temperature of 5 ℃ for reaction for 24 hours to obtain an intermediate 2, the intermediate 2 is completely added into the intermediate 1, 10.8 g (0.60mol) of water is added, and the reaction is carried out for 15 hours at the temperature of 5 ℃; then theNeutralizing the obtained mixture with hydrochloric acid, adding 60mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with a structure shown as formula (1), wherein R is1＝R2Is methyl, R3-R10Is phenyl, A1-A6For phenyl, m ═ 1, n ═ 12, and the yield obtained was 96%.
The obtained siloxane bridging silane end-capped siloxane bridging ladder-shaped polysiloxane is colorless transparent solid, the average value of the polymerization degree n is 12, the refractive index is 1.55(25 ℃), the glass transition temperature is 34.31 ℃, 230 ℃, and the viscosity is 973 Poise (Poise) at the rotating speed of 100 rpm. The air thermal oxidation resistance is respectively as follows: the hydroxyl-terminated ladder-shaped polymer 4HO-blocked Me-SLPS does not discolor or crosslink at 300 ℃ for 15 h; while the corresponding monofunctional silane (e.g. diphenylmethylsilyl) end-capped siloxane-bridged ladder polysiloxane MePh2SiO-I-blocked Me-SLPS is not crosslinked and does not change color at 300 ℃ for 15 h. And the corresponding diphenylsiloxane bridging silane-terminated siloxane bridging ladder polysiloxane Ph2The I-Me-SLPS shows better performance, and does not crosslink and discolor at 300 ℃ for 24 hours.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.12,7.14-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-65.28,-43.35ppm。
Example 4: PhMe-I-Me-SLPS Synthesis
The siloxane-bridged silane-terminated ladder polysiloxanes were prepared from methyltrimethoxysilane, methylphenyldimethoxysilane and diphenylsilanediol.
Under the protection of dry nitrogen, placing 27.2 g of methyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.10mol) and 20 g of N, N-dimethylformamide into a three-neck flask provided with a mechanical stirrer, a constant-pressure dropping funnel and a reflux condenser, uniformly stirring at room temperature, adding 0.10 g of ethanolamine at the temperature of-10 ℃, and reacting for 8 hours to obtain an intermediate 1; while in another three-neck flask equipped with mechanical stirring, constant pressure dropping funnel and reflux condenser under dry nitrogen protection, 0.81 g of methylphenyldimethoxysilane (0.0044mol), 2 g of N, N-dimethylformamide and 0.476 g of diphenylsilanediol (0.0022mol) were added and stirred uniformlyAdding 0.02 g of ethanolamine at 0 ℃ for reacting for 18 hours to obtain an intermediate 2, completely adding the intermediate 2 into the intermediate 1, adding 7.2 g (0.40mol) of water, reacting for 5 hours at-5 ℃, and vacuumizing for reacting for 12 hours; then neutralizing the obtained mixture with hydrochloric acid, adding 40mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with a structure shown as formula (1), wherein R is1＝R2＝R5＝R6＝R9＝R10Is methyl, R3＝R4＝R7＝R8Is phenyl, A1-A6For phenyl, m ═ 1, n ═ 80, and the yield obtained was 94%.
The obtained siloxane bridging silane end-capped siloxane bridging ladder-shaped polysiloxane is colorless transparent solid, the average value of the polymerization degree n is 80, the refractive index is 1.54(25 ℃), the glass transition temperature is 28.51 ℃, 230 ℃, and the viscosity is 365 Poise (Poise) at the rotating speed of 50 rpm. The air thermal oxidation resistance is respectively as follows: the hydroxyl-terminated ladder-shaped polymer 4HO-blocked Me-SLPS does not discolor or crosslink at 300 ℃ for 15 h; while the corresponding monofunctional silane (e.g. dimethylphenylsilyl) end-blocks the siloxane bridge ladder polysiloxane Me2PhSiO-I-blocked Me-SLPS does not crosslink and change color at 300 ℃ for 15 h. The corresponding methyl phenyl siloxane bridging group silane end-blocked siloxane bridging group ladder-shaped polysiloxane PhMe-I-Me-SLPS shows better performance and does not crosslink and discolor at 300 ℃ multiplied by 24 hours.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.12,7.14-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-64.32,-43.02,-28.73ppm。
Example 5: synthesis of MeEpoxy-I-Ph-SLPS
Siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxanes were prepared from phenyltrimethoxysilane, 3- ((2,3) -glycidoxy) propylmethyldiethoxysilane and diphenylsilanediol.
39.7 g of phenyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.10mol) and 10 g of acetone are placed in a three-neck flask with mechanical stirring, a constant-pressure dropping funnel and a reflux condenser under the protection of dry nitrogen, stirred uniformly at room temperature and 0.3 g of acetone is added at 0 DEG CReacting ammonia water with styrene-divinylbenzene copolymer as a matrix for 15 hours to obtain an intermediate 1; simultaneously adding 23.6 g of 3- ((2,3) -glycidoxy) propylmethyldiethoxysilane (0.10mol), 20 g of acetone and 10.8 g of diphenylsilanediol (0.05mol) into another three-neck flask which is protected by dry nitrogen and is provided with a mechanical stirring, a constant pressure dropping funnel and a reflux condenser, uniformly stirring, adding 0.60 g of ammonia water at 10 ℃ for reacting for 20 hours to obtain an intermediate 2, completely adding the intermediate 2 into the intermediate 1, adding 27.0 g (1.50mol) of water, and reacting for 20 hours at 0 ℃; then neutralizing the obtained mixture with hydrochloric acid, adding 40ml of toluene, washing with water, separating, and concentrating under reduced pressure to obtain siloxane-bridged silane-terminated ladder-shaped polysiloxane with a structure of formula (1), wherein R is1＝R2Is phenyl, R3＝R4＝R7＝R8Is methyl, R5＝R6＝R9＝R10Is 3- ((2,3) -glycidoxy) propyl, A1-A6For phenyl, m ═ 1, n ═ 34, and the yield obtained was 92%.
The obtained siloxane bridging silane end-capped siloxane bridging trapezoidal polysiloxane is colorless and transparent solid, the average value of the polymerization degree n is 34, the refractive index is 1.56(25 ℃), and the glass transition temperature is 40.28 ℃. TGA determined a 5% thermal decomposition temperature of 400 ℃. The viscosity was 8550 Poise (Poise) at 230 ℃ and 30 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.12,0.21-0.44,1.41-1.73,2.52-3.64,7.02-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-78.6,-45.16,-17.87ppm。
Example 6: MeVi-I-Ph-SLPS Synthesis
Silane-terminated siloxane-bridged ladder polysiloxanes are prepared from phenyltrimethoxysilane, methylvinyldimethoxysilane and diphenylsilanediol.
39.7 g of phenyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.10mol) and 30 g of diethylene glycol dimethyl ether are placed in a three-neck flask with mechanical stirring, a constant pressure dropping funnel and a reflux condenser under the protection of dry nitrogen, stirred uniformly at room temperature, and 0.30 g of 1, 8-diazabicyclo [5.4.0] is added at-20 DEG C]Reacting for 5 hours to obtain an intermediate 1; at the same time, 8.8 g of methylvinyldimethoxysilane (0.067mol), 40 g of diethylene glycol dimethyl ether and 7.2 g of diphenylsilanediol (0.033mol) were added to another three-necked flask equipped with a mechanical stirrer, a constant pressure dropping funnel and a reflux condenser under protection of dry nitrogen, stirred uniformly, and 0.30 g of 1, 8-diazabicyclo [5.4.0] was added at-20 ℃]Undec-7-ene reacts for 12 hours to obtain an intermediate 2, the intermediate 2 is added into the intermediate 1, 33.6 g (1.86mol) of water is added, and the reaction is carried out for 15 hours at the temperature of 0 ℃; then neutralizing the obtained mixture with hydrochloric acid, adding 50mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with the structure of formula (1), wherein R is3＝R4＝R7＝R8Is vinyl, R1＝R2Is phenyl, R5＝R6＝R9＝R10Is methyl, A1-A6For phenyl, m ═ 1, n ═ 6, and the yield obtained was 83%.
The obtained siloxane bridging silane end-capped siloxane bridging trapezoidal polysiloxane is colorless transparent soft solid, the average value of the polymerization degree n is 6, and the refractive index is 1.57(25 ℃). The glass transition temperature was 28.83 ℃ as compared to 0.47 ℃ for the product dimethylvinyl terminated phenyl homopolymer. TGA determined a 5% thermal decomposition temperature of 390 ℃ and a comparative product, a dimethylvinyl terminated phenyl homopolymer, had a 5% thermal decomposition temperature of 330 ℃. The viscosity was 1973 Poise (Poise) at 230 ℃ and 100 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.13,5.51-6.02,7.01-7.56ppm；29Si NMR(80MHz,CDCl3,298K):δ-78.27,-44.75,-32.76ppm。
Example 7: MeVi-I-Me-SLPS Synthesis
The siloxane-bridged silane-terminated ladder polysiloxanes were prepared from methyltrimethoxysilane, methylvinyldimethoxysilane and diphenylsilanediol.
27.2 g of methyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.10mol) and 20 g of cyclohexane were placed under a protective atmosphere of dry nitrogen in a dropping funnel equipped with mechanical stirring and at constant pressure and cooled under refluxIn a three-necked flask of a condenser, the mixture was stirred at room temperature, and 0.40 g of 1, 5-diazabicyclo [4.3.0] was added thereto at-10 ℃]-5-nonene, reacting for 8 hours to obtain intermediate 1; while in another three-necked flask equipped with mechanical stirring, constant pressure dropping funnel and reflux condenser, while being protected with dry nitrogen, 21.9 g of methylvinyldimethoxysilane (0.17mol), 30 g of dioxane and 18 g of diphenylsilanediol (0.083mol) were added and stirred uniformly, 0.40 g of 1, 5-diazabicyclo [4.3.0] was added at 0 deg.C]-5-nonene, reacting for 18 hours to obtain an intermediate 2, adding all the intermediate 2 into the intermediate 1, adding 18 g (1.0mol) of water, adding 20 g of diethylene glycol dimethyl ether, and reacting for 15 hours at 0 ℃; then neutralizing the obtained mixture with hydrochloric acid, adding 35mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with the structure of formula (1), wherein R is1＝R2＝R3＝R4＝R7＝R8Is methyl, R5＝R6＝R9＝R10Is vinyl, A1-A6For phenyl, m ═ 1, n ═ 12, and the yield obtained was 97%.
The obtained siloxane-bridged-group silane-terminated siloxane-bridged-group ladder-shaped polysiloxane is a colorless transparent solid, the average value of the polymerization degree n is 12, the refractive index is 1.53(25 ℃), and the glass transition temperature is 47.51 ℃. Viscosity was 718 Poise (Poise) at 230 ℃ and 100 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.11,5.51-6.02,7.02-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-65.12,-44.47,-31.87ppm。
Example 8: synthesis of MeEpoxy-I-Vi-SLPS
Siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxanes were prepared from vinyltrimethoxysilane, 3- ((2,3) -glycidoxy) propylmethyldiethoxysilane and diphenylsilanediol.
29.7 g of vinyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.10mol) and 5 g of N, N-dimethylformamide were placed in a three-necked flask equipped with mechanical stirring, a constant-pressure dropping funnel and a reflux condenser under the protection of dry nitrogen, stirred uniformly at room temperature, and then the mixture was cooled to room temperatureAdding 2 g of diethanolamine at the temperature of 5 ℃, and reacting for 16 hours to obtain an intermediate 1; simultaneously adding 4.97 g of 3- ((2,3) -glycidoxy) propylmethyldiethoxysilane (0.02mol), 10 g of N, N-dimethylformamide and 2.2 g of diphenylsilanediol (0.01mol) into another three-neck flask which is protected by dry nitrogen and is provided with a mechanical stirring, a constant pressure dropping funnel and a reflux condenser, uniformly stirring, adding 0.40 g of diethanolamine at 10 ℃, reacting for 18 hours to obtain an intermediate 2, completely adding the intermediate 2 into the intermediate 1, adding 9 g (0.50mol) of water, adding 5 g of N, N-dimethylformamide, and vacuumizing at 5 ℃ for reacting for 15 hours; then neutralizing the obtained mixture with formic acid, adding 40mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with the structure of formula (1), wherein R is1＝R2Is vinyl, R3＝R4＝R7＝R8Is methyl, R5＝R6＝R9＝R10Is 3- ((2,3) -glycidoxy) propyl, A1-A6For phenyl, m ═ 1, n ═ 15, and the yield obtained was 77%.
The obtained siloxane-bridged siloxane-terminated trapezoidal polysiloxane is a colorless transparent solid, the average value of the polymerization degree n is 15, the refractive index is 1.55(25 ℃), and the glass transition temperature is 34.66 ℃. The viscosity was 3701 Poise (Poise) at 230 ℃ and 50 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.13,0.24-0.43,1.40-1.74,2.52-3.62,5.55-6.02,7.14-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-79.46,-44.87,-17.94ppm。
Example 9: MeAcryl-I-Me-SLPS Synthesis
The siloxane-bridged silane-terminated ladder polysiloxanes were prepared from methyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and diphenylsilanediol.
Under the protection of dry nitrogen, 27.2 g of methyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.10mol) and 25 g of dioxane were placed in a three-neck flask equipped with a mechanical stirrer, a constant pressure dropping funnel and a reflux condenser, and stirred uniformly at room temperatureAdding 0.20 g of ethanolamine at the temperature of 30 ℃ and reacting for 16 hours to obtain an intermediate 1; simultaneously, 3.9 g of 3-methacryloxypropyl methyldimethoxysilane (0.017mol), 10 g of dioxane and 1.8 g of diphenyl silanediol (0.0083mol) are added into another three-neck flask which is provided with a dry nitrogen protection device, a mechanical stirring device, a constant pressure dropping funnel and a reflux condenser and are uniformly stirred, 0.04 g of ethanolamine is added at the temperature of minus 20 ℃ for reacting for 18 hours to obtain an intermediate 2, 12.6 g of water (0.70mol) is added into the intermediate 1 at the temperature of minus 20 ℃, the intermediate 2 is added into the mixed solution of the intermediate 1 and the water in drops, and the reaction is continued for 10 hours after 3 hours of dropping; then neutralizing the obtained mixture with formic acid, adding 50mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with the structure of formula (1), wherein R is1＝R2＝R3＝R4＝R7＝R8Is methyl, R5＝R6＝R9＝R10Is 3-methacryloxypropyl, A1-A6For phenyl, m ═ 1, n ═ 120, and the yield obtained was 87%.
The obtained siloxane-bridged siloxane-terminated silane-bridged trapezoidal polysiloxane is colorless transparent viscous liquid, the average value of the degree of polymerization n is 120, the refractive index is 1.53(25 ℃), and the glass transition temperature is 10.32 ℃. The viscosity was 9490 Poise (Poise) at 230 ℃ and 30 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.11,-0.25-0.66,1.72-1.91,5.51-5.53,5.98-6.04,7.02-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-65.02,-45.15,-17.94ppm。
Example 10: me2Synthesis of-I-Ph/Acryl-SLPS
The siloxane-bridged silane-terminated ladder polysiloxanes were prepared from 3- (methacryloyloxy) propyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane and diphenylsilanediol.
19.8 g of phenyltrimethoxysilane (0.10mol), 24.8 g of 3- (methacryloyloxy) propyltrimethoxysilane (0.10mol), 21.6 g of diphenylsilanediol (0.10mol) and 40 g of diethylene glycol dimethyl ether were placed in a dry nitrogen atmosphereIn a three-neck flask provided with a mechanical stirring device, a constant pressure dropping funnel and a reflux condenser, stirring uniformly at room temperature, adding 0.20 g of tetramethylammonium hydroxide at the temperature of minus 20 ℃, and reacting for 14 hours to obtain an intermediate 1; simultaneously, 0.15 g of dimethyldimethoxysilane (0.0012mol), 5 g of diethylene glycol dimethyl ether and 0.14 g of diphenylsilanediol (0.00062mol) are added into another three-neck flask which is provided with a dry nitrogen protection device, a mechanical stirring device, a constant pressure dropping funnel and a reflux condenser and are uniformly stirred, 0.02 g of tetramethylammonium hydroxide is added at the temperature of minus 20 ℃ for reacting for 18 hours to obtain an intermediate 2, the intermediate 2 is completely added into the intermediate 1,9 g of water (0.50mol) is added, and the reaction is carried out for 5 hours at the temperature of minus 20 ℃; then neutralizing the obtained mixture with hydrochloric acid, adding 80mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with the structure of formula (1), wherein R is1Is 3- (methacryloyloxy) propyl, R2Is phenyl, R3＝R4＝R7＝R8＝R5＝R6＝R9＝R10Is methyl, A1-A6For phenyl, m ═ 1, n ═ 300, and the yield obtained was 87%.
The obtained siloxane-bridged-group silane-terminated siloxane-bridged-group trapezoidal polysiloxane is colorless transparent viscous liquid, the average value of the degree of polymerization n is 300, the refractive index is 1.53(25 ℃), and the glass transition temperature is-12.34 ℃. The viscosity was 61.62 Poise (Poise) at 230 ℃ and 100 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.11,0.64-0.66,1.72-1.91,5.51-5.53,5.99-6.03,7.02-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-79.22,-64.85,-45.21,-18.02ppm。
Example 11: ph2Synthesis of-I-Vi/Epoxy-SLPS
Siloxane-bridged silane-terminated ladder polysiloxanes were prepared from 3- ((2,3) -glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, diphenyldimethoxysilane and diphenylsilanediol.
14.82 g of phenyltrimethoxysilane (0.10mol), 23.6 g of 3- ((2,3) -glycidoxy) propyltrimethoxysilane (0.10 m) were placed under a dry nitrogen blanketol), 21.6 g of diphenyl silanediol (0.10mol) and 10 g of tetrahydrofuran are placed in a three-neck flask provided with a mechanical stirring, constant pressure dropping funnel and a reflux condenser, the mixture is uniformly stirred at room temperature, 0.70 g of DBN is added at the temperature of 0 ℃, and the reaction is carried out for 10 hours to obtain an intermediate 1; simultaneously, 0.92 g of diphenyldimethoxysilane (0.0038mol), 2 g of trichloromethane and 0.40 g of diphenylsilanediol (0.0019mol) are added into another three-neck flask which is protected by dry nitrogen and is provided with a mechanical stirrer, a constant pressure dropping funnel and a reflux condenser, the mixture is uniformly stirred, 0.02 g of DBN is added at the temperature of 0 ℃ for reacting for 18 hours to obtain an intermediate 2, the intermediate 2 is completely added into the intermediate 1,8 g of water (0.44mol) is added, and the reaction is carried out for 15 hours at the temperature of minus 10 ℃; then neutralizing the obtained mixture with hydrochloric acid, adding 30mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with the structure of formula (1), wherein R is1Is 3- ((2,3) -glycidoxy) propyl, R2Is vinyl, R3＝R4＝R7＝R8＝R5＝R6＝R9＝R10Is phenyl, A1-A6For phenyl, m ═ 1, n ═ 90, and the yield obtained was 80%.
The obtained siloxane-bridged silane-terminated ladder-shaped polysiloxane is colorless transparent viscous liquid, the average value of the polymerization degree n is 90, the refractive index is 1.55(25 ℃), and the glass transition temperature is-3.4 ℃. The viscosity was 94.54 Poise (Poise) at 230 ℃ and 100 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.04-0.13,0.20-0.41,1.40-1.73,2.52-3.64,7.02-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-78.72,-64.18,-45.28ppm。
Example 12: MePh-I-AE/AP-SLPS
By reacting N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, methylphenyldimethoxysilane and HO (Ph)2SiO)2And H, preparing siloxane bridging silane end-capped siloxane bridging trapezoidal polysiloxane.
44.5 g of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (0.20mol), 41.4 g of HO (Ph) were added under a dry nitrogen blanket2SiO)2H (0.10mol) and 40 g of tetrahydrofuran are placed inIn a three-neck flask provided with a mechanical stirring device, a constant pressure dropping funnel and a reflux condenser, stirring uniformly at room temperature, adding 0.20 g of pyridine at 0 ℃, and reacting for 6 hours to obtain an intermediate 1; while in another three-necked flask equipped with a mechanical stirrer, a constant pressure dropping funnel and a reflux condenser under a dry nitrogen blanket were charged 11.5 g of methylphenyldimethoxysilane (0.063mol), 20 g of tetrahydrofuran, 12.9 g of HO (Ph)2SiO)2H (0.031mol) is stirred evenly, 0.20 g triethanolamine is added at 0 ℃ to react for 13 hours to obtain an intermediate 2, the intermediate 2 is added into the intermediate 1,9 g water (0.50mol) is added to react for 15 hours at-10 ℃; then neutralizing the obtained mixture with hydrochloric acid, adding 40mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with a structure shown as formula (1), wherein R is1＝R2Is N- (2-aminoethyl) -3-aminopropyl, R3＝R4＝R7＝R8Is methyl, R5＝R6＝R9＝R10Is phenyl, A1-A6For phenyl, m ═ 2, n ═ 320, and the yield obtained was 86%.
The obtained siloxane-bridged-group silane-terminated siloxane-bridged-group ladder-shaped polysiloxane is colorless transparent viscous liquid, the average value of the polymerization degree n is 320, the refractive index is 1.53(25 ℃), and the glass transition temperature is-37.3 ℃. The viscosity was 32.65 Poise (Poise) at 230 ℃ and 100 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.04-0.13,1.15-1.22,2.52-2.58,3.70-3.85,7.02-7.53ppm；29Si NMR(80MHz,CDCl3,298K):δ-64.67,-44.81,-28.65ppm。
Example 13: synthesis of MeEpoxy-I-Pr-SLPS
Siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxanes were prepared from propyltrimethoxysilane, 3- ((2,3) -glycidoxy) propylmethyldiethoxysilane, dimethyldimethoxysilane and diphenylsilanediol.
32.9 g of propyltrimethoxysilane (0.20mol), 21.6 g of diphenylsilanediol (0.10mol) and 10 g of dioxane were placed under a protective atmosphere of dry nitrogen in a dropping funnel equipped with mechanical stirring and at constant pressure and cooled under refluxUniformly stirring at room temperature in a three-neck flask of a condenser, adding 0.20 g of triethylamine at-5 ℃, and reacting for 12 hours to obtain an intermediate 1; simultaneously, 3.3 g of 3- ((2,3) -glycidoxy) propylmethyldiethoxysilane (0.013mol), 1.6 g of dimethyldimethoxysilane (0.013mol), 2.9 g of diphenylsilanediol (0.013mol) and 10 g of dioxane are added into another three-neck flask which is protected by dry nitrogen and is provided with a mechanical stirring device, a constant pressure dropping funnel and a reflux condenser, and are uniformly stirred, 0.2 g of triethylamine is added at the temperature of-5 ℃ to react for 16 hours to obtain an intermediate 2, the intermediate 2 is completely added into the intermediate 1, 12.6 g (0.70mol) of water is added, and the reaction is carried out at the temperature of 0 ℃ for 10 hours; then neutralizing the obtained mixture with hydrochloric acid, adding 30mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with the structure of formula (1), wherein R is1＝R2Is propyl, R3＝R4＝R5＝R7＝R8＝R9Is methyl, R6＝R10Is 3- ((2,3) -glycidoxy) propyl, A1-A6For phenyl, m ═ 1, n ═ 75, and the yield obtained was 89%.
The obtained siloxane-bridged-group silane-terminated siloxane-bridged-group ladder-shaped polysiloxane is a colorless transparent solid, the average value of the polymerization degree n is 75, the refractive index is 1.53(25 ℃), and the glass transition temperature is 27.54 ℃. Viscosity was 8490 Poise (Poise) at 230 ℃ and 30 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.04-0.13,0.19-0.41,1.42-1.74,2.52-3.64,7.01-7.57ppm；29Si NMR(80MHz,CDCl3,298K):δ-64.85,-45.24,-18.32ppm。
Example 14: ph2-I-Me-SLBuS Synthesis
Siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxanes are prepared from methyltrimethoxysilane, diphenyldimethoxysilane and diisobutylsilyldiol.
27.2 g of methyltrimethoxysilane (0.20mol), 17.6 g of diisobutylsilylene glycol (0.10mol) and 20 g of chloroform were placed in a three-necked flask equipped with a mechanical stirrer, a dropping funnel at constant pressure and a reflux condenser under protection of dry nitrogen and stirred uniformly at room temperatureAdding 0.08 g of liquid ammonia at the temperature of minus 20 ℃ and reacting for 6 hours to obtain an intermediate 1; meanwhile, 48.9 g of diphenyldimethoxysilane (0.20mol), 40 g of trichloromethane and 17.6 g of diisobutylsilylene glycol (0.10mol) are added into another three-neck flask which is provided with a mechanical stirring device, a constant pressure dropping funnel and a reflux condenser under the protection of dry nitrogen and are uniformly stirred, 0.30 g of liquid ammonia is added at 0 ℃ for reaction for 20 hours to obtain an intermediate 2, the intermediate 2 is completely added into the intermediate 1, 10.8 g (0.60mol) of water is added, and the reaction is carried out for 10 hours at 0 ℃; then neutralizing the obtained mixture with hydrochloric acid, adding 40mL of toluene, washing with water, separating, and concentrating under reduced pressure to obtain siloxane-bridged-silane-terminated siloxane-bridged ladder-shaped polysiloxane with a structure shown as formula (1), wherein R is1＝R2Is methyl, R3-R10Is phenyl, A1-A6For isobutyl, m ═ 1, n ═ 12, and the yield obtained was 94%.
The obtained siloxane bridging silane end-capped siloxane bridging ladder-shaped polysiloxane is colorless transparent solid, the average value of the polymerization degree n is 12, the refractive index is 1.52, the glass transition temperature is 14.82 ℃, the viscosity is 345 Poise (Poise) at the temperature of 210 ℃ and the rotating speed of 100 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.12,0.89-1.02,1.52-1.71,7.12-7.51ppm；29Si NMR(80MHz,CDCl3,298K):δ-63.28,-44.23,-21.25ppm。
Example 15: me2-I-Me-SLPrS Synthesis
Siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxanes were prepared from methyltrimethoxysilane, dimethyldimethoxysilane and dipropylene-silanediol.
Under the protection of dry nitrogen, placing 27.2 g of methyltrimethoxysilane (0.20mol), 14.8 g of dipropylene silanediol (0.10mol) and 15 g of N, N-dimethylformamide into a three-neck flask provided with a mechanical stirring device, a constant-pressure dropping funnel and a reflux condenser, uniformly stirring at room temperature, adding 0.10 g of DBU at the temperature of-10 ℃, and reacting for 10 hours to obtain an intermediate 1; while in another three-necked flask equipped with a mechanical stirrer, a constant pressure dropping funnel and a reflux condenser, under a dry nitrogen blanket, 0.53 g of dimethylphenyldimethoxysilane (0.0044mol), 2 g of N, N-dimethylmethane were placedAmide and 0.33 g of dipropyl silanediol (0.0022mol) are stirred uniformly, 0.02 g of DBU is added at 0 ℃ to react for 20 hours to obtain an intermediate 2, the intermediate 2 is added into the intermediate 1 completely, 7.2 g (0.40mol) of water is added, then the obtained mixture is neutralized by hydrochloric acid, 40mL of toluene is added, and the mixture is washed by water, separated and concentrated under reduced pressure to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane with the structure of formula (1), wherein R is1-R10Is methyl, A1-A6For propyl, m ═ 1, n ═ 450, and the yield obtained was 92%.
The obtained siloxane bridging silane end-capped siloxane bridging ladder-shaped polysiloxane is colorless transparent solid, the average value of the polymerization degree n is 450, the refractive index is 1.52(25 ℃), the glass transition temperature is 13.51 ℃, the viscosity is 134 Poise (Poise) at the rotating speed of 50 rpm.1H NMR(400MHz,CDCl3,298K):δ-0.06-0.11ppm；29Si NMR(80MHz,CDCl3,298K):δ-56.43,-21.73ppm。
While the present invention has been described in detail with reference to the specific embodiments and examples, it will be apparent to those skilled in the art that various changes, modifications, substitutions and the like can be made in the embodiments and examples without departing from the spirit and essential characteristics of the present invention. Embodiments obtained by modification, correction, and replacement are also within the scope of the present invention.
Claims (9)
1. A siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane, characterized in that it has a molecular structure represented by the following formula (1):
wherein:
m is an integer of 1 to 10,
n is an integer of 1 to 1000,
A1、A2、A3、A4、A5、A6each independently selected from hydrogen, substituted or unsubstituted straight, branched or cyclic C1-25Alkyl, substituted or unsubstituted straight, branched or cyclic C2-25Alkenyl, substituted or unsubstituted C5-25An aryl group, a heteroaryl group,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10each independently selected from hydrogen, hydroxy, substituted or unsubstituted straight, branched or cyclic C1-25Alkyl, substituted or unsubstituted straight, branched or cyclic C2-25Alkenyl, substituted or unsubstituted C5-25Aryl, substituted or unsubstituted, straight, branched or cyclic C1-25Alkoxy, substituted or unsubstituted C5-25An aryloxy group which is a group having a lower alkoxy group,
when the above group has a substituent, the substituent is at least one selected from the group consisting of: straight, branched or cyclic C1-25Alkyl, straight, branched or cyclic C2-25Alkenyl radical, C5-25An aryl group, a group containing at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom, a halogen atom,
each of the above alkyl group, alkoxy group, alkenyl group, aryl group and aryloxy group may have at least one hetero atom selected from the group consisting of O, S, P, N as a chain constituting atom or a ring constituting atom in a chain or a ring.
2. The siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxane of claim 1,
the group containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom is selected from the group consisting of a hydroxyl group, a glycidoxy group, C5-25Epoxycycloalkyl, acryloxy, C1-25Alkyl-substituted acryloxy, mercapto, amino-straight, branched or cyclic C1-25Alkyl radical, C6-25Arylamino, cyano, ureido, phosphino.
3. According to the claimsThe siloxane-bridged silane-terminated siloxane-bridged ladder polysiloxane of claim 1, wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、A1、A2、A3、A4、A5、A6Each independently selected from the group consisting of hydrogen, hydroxy, methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, tert-butyl, N-hexyl, cyclohexyl, N-octyl, N-decyl, N-dodecyl, N-hexadecyl, N-octadecyl, N-docosyl, vinyl, allyl, phenyl, methylphenyl, chlorophenyl, p-vinylphenyl, 3- (2, 3-epoxypropoxy) propyl, 2- (3, 4-epoxycyclohexyl) ethyl, acryloxypropyl, 3-methacryloxypropyl, mercaptopropyl, aminopropyl, 3- (2-aminoethyl) -aminopropyl, 4-amino-3, 3-dimethylbutyl, N-N-butyl-3-aminopropyl, 2-cyanoethyl, 3-cyanopropyl, 3,3, 3-trifluoropropyl group, 1H,2H, 2H-perfluorooctyl group, 1H,2H, 2H-perfluorodecyl group, chloropropyl group, ureidopropyl group, methoxy group and ethoxy group.
4. A method for preparing siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane according to claim 1, wherein a tetrafunctional I-shaped siloxane-bridged siloxane monomer (2) is co-hydrolyzed with bifunctional I-shaped siloxane-bridged-silane capping agents (3) and (4), and a ladder superstructure is formed by virtue of the synergistic action of supermolecular weak bonds to regulate and control polymerization and capping reactions to obtain the siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane with the structure of formula (1); the tetrafunctional I-shaped siloxane bridging group siloxane monomer (2) is represented by a structural formula (2)
Wherein,
m、R1、R2、A1、A2are each defined and claimedThe same as defined in claim 1;
x is selected from OH, halogen, C1-25Alkoxy or C1-25One of acyloxy groups;
the bifunctional I-shaped siloxane bridging silane end-capping agent (3) is represented by a structural formula (3)
Wherein,
m、R3、R4、R5、R6、A3、A4are each as defined in claim 1;
x is selected from OH, halogen, C1-25Alkoxy or C1-25One of acyloxy groups;
the bifunctional I-shaped siloxane bridging silane end-capping agent (4) is represented by a structural formula (4)
Wherein,
m、R7、R8、R9、R10、A5、A6are each as defined in claim 1;
x is selected from OH, halogen, C1-25Alkoxy or C1-25One of the acyloxy groups.
5. The method of preparing a siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane of claim 4, characterized by comprising the steps of:
adding silane with structural formulas (2), (3) and (4), organic solvent, water and catalyst into a reactor to carry out hydrolysis and condensation reaction, and continuously or discontinuously vacuumizing to remove condensation byproducts; and then separating and purifying the product obtained by the reaction to obtain the siloxane-bridged group ladder-shaped polysiloxane with the structure of the formula (1) and terminated by siloxane-bridged group silane.
6. The method of producing a siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane according to claim 5,
the tetrafunctional I-shaped monomer of the formula (2) is prepared by condensing a trifunctional silane coupling agent and silicon glycol in the presence of a catalyst,
the trifunctional silane coupling agent is represented by the formula RSiX3It is shown that,
wherein R ═ R1Or R2(ii) a X is halogen, C1-25Alkoxy radical, C1-25And (4) acyloxy.
7. The method of producing a siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane according to claim 5,
the bifunctional I-shaped siloxane bridging group silane end-capping agents (3) and (4) are prepared by condensing a bifunctional silane coupling agent and silicon glycol in the presence of a catalyst,
the bifunctional silane coupling agent is represented by the formula R' SiX2Is represented by R', R ″ -, R ″3And R5Combination, R4And R6Combination or R7And R9Combination, R8And R10Combining; x is halogen, C1-25Alkoxy radical, C1-25And (4) acyloxy.
8. The method for preparing a siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane according to claim 5, wherein said organic solvent is selected from the group consisting of: one or more of alkanes, substituted alkanes, alcohols, ethers, ketones, esters, amides, nitriles, pyrrolidones, sulfoxides.
9. The method of producing a siloxane-bridged-silane-terminated siloxane-bridged ladder polysiloxane according to claim 5,
the catalyst is one or more selected from acid, oxide and hydroxide, ammonia or amine, transition metal compound and ion exchange resin.
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