CN105330865B - A kind of synthetic method of catenne shape polysiloxanes - Google Patents
A kind of synthetic method of catenne shape polysiloxanes Download PDFInfo
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- -1 polysiloxanes Polymers 0.000 title claims abstract description 97
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 76
- 238000010189 synthetic method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 7
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical class O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 claims description 4
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical class O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 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 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003863 metallic catalyst Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000000232 haloalkynyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- XBBXDTCPEWHXKL-UHFFFAOYSA-N rhodium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Rh+3].[Rh+3] XBBXDTCPEWHXKL-UHFFFAOYSA-N 0.000 description 1
- MHOVAHRLVXNVSD-OIOBTWANSA-N rhodium-100 Chemical compound [100Rh] MHOVAHRLVXNVSD-OIOBTWANSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The present invention relates to polysiloxanes synthesis technical field, to solve the problems, such as there is no practicable synthetic technology present in existing catenne shape polysiloxanes research, the present invention proposes a kind of synthetic method of catenne shape polysiloxanes, using small annular siloxane and water as raw material, and in the presence of metallic catalyst, reacted in organic solvent, pass through last handling process again, obtain catenne shape polysiloxanes, the present invention realizes efficiently synthesizing for catenne shape polysiloxanes, yield can reach 60~95%, product has heat endurance good, and reaction condition is gentle, it is applied widely, energy consumption is low, combined coefficient is high, raw material is cheap and easy to get, the advantages that product purification process is simple and easy.
Description
Technical field
The present invention relates to polysiloxanes synthesis technical field, more particularly to a kind of efficiently synthesizing for catenne shape polysiloxanes
Method.
Background technology
Catenne shape polysiloxanes has important use, is such as used for molecular recognition, synthesis of super branched gathers with special construction
Siloxanes, fire resistant polymer is prepared with developing novel silane coupler etc..So far, only document proposes catenne shape
The concept of polysiloxanes, not practicable synthetic method realize the synthesis of catenne shape polysiloxanes.
Nineteen fifty-three, Frisch, Martin and Mark speculate why high molecular weight silicone has liquid or wax-like
Outward appearance, be due in polysiloxanes contain catenne shape polysiloxanes caused by, these catenne shape polysiloxanes act as being plasticized
The effect (Monatsh.Chem.1953,84,250-256) of agent, but this hypothesis does not obtain experiment and confirmed.
Bannister and Semlyen proposes the big ring-like poly- silicon of heating in the heat endurance of the big ring-like polysiloxanes of research
Oxygen alkane may form catenne shape polysiloxanes (Polymer 1981,22,377-381), and same they simply propose one kind
Conjecture, data do not support them to obtain catenne shape polysiloxanes really.
The current report about catenne shape polysiloxanes is also merely resting on concept and the conjecture stage of proposing, unactual
Feasible synthetic method obtains catenne shape polysiloxanes.
The content of the invention
To solve the problems, such as there is no practicable synthetic technology, this hair present in existing catenne shape polysiloxanes research
It is bright to propose a kind of synthetic method of catenne shape polysiloxanes, with reaction condition is gentle, applied widely, energy consumption is low, synthesis
The advantages that efficiency high, raw material are cheap and easy to get, product purification process is simple and easy.
The present invention is achieved by the following technical solutions：A kind of synthetic method of catenne shape polysiloxanes is with small ring-type
Siloxanes and water are raw material, and in the presence of metallic catalyst, are reacted in organic solvent, then by post-processing
Journey, obtains catenne shape polysiloxanes, and the present invention realizes efficiently synthesizing for catenne shape polysiloxanes, and yield can reach 60~
95%, product has the advantages that heat endurance is good.
Course of reaction is as follows：
Wherein, R1、R2、R3、R4Separately selected from hydrogen, fluorine, alkyl, alkenyl, alkynyl, aromatic radical, epoxy radicals, ester group,
A kind of in sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl, m, n, p, q are respectively to be more than or equal to 0
Integer, x is integer more than 0.
Described small annular siloxane is one or more of in cyclotrisiloxane, cyclotetrasiloxane, D5.It is small
The mass ratio of annular siloxane and water is 1: 0.001~1.
Described metallic catalyst is a kind of in metal simple-substance, metal oxide, metal salt, complex compound.Small ring silica
The mass ratio of alkane and metallic catalyst is 1: 0.0001~0.1.Preferably, metallic catalyst be selected from all metals simple substance or
The corresponding compound of person, more preferably from iron, cobalt, nickel, ruthenium, rhodium, platinum, palladium, gold, silver, copper, tin, titanium, pick, chromium, manganese, lanthanide series metal
A kind of simple substance of middle metal or corresponding compound.
Organic solvent is one or more of in alkane, aromatic hydrocarbon, ethers, cyclic ethers class, ketone.Amount used is to make solute
The amount of dissolving.Preferably, organic solvent is selected from hexane, hexamethylene, toluene, ether, butyl ether, tetrahydrofuran, dioxane, third
It is one or more of in ketone, methyl iso-butyl ketone (MIBK).
Reaction temperature is -75~140 DEG C, and the reaction time is 10 minutes~24 hours.
Last handling process is vacuum drying, absorption, precipitation or recrystallization.
The present invention using small annular siloxane (such as cyclotrisiloxane, cyclotetrasiloxane and D5), water as raw material,
In the presence of metallic catalyst, polymerisation occurs, realizes efficiently synthesizing for catenne shape polysiloxanes.Product structure passes through red
External spectrum, hydrogen spectrum nuclear magnetic resonance, silicon spectrum nuclear magnetic resonance, chemical method end-group analysis and rheology etc. have carried out structural characterization, pass through
Thermogravimetic analysis (TGA) have studied the heat endurance of product.Infrared spectrum, hydrogen spectrum nuclear magnetic resonance, silicon spectrum nuclear magnetic resonance, chemical method end group
Analysis etc. proves that product does not contain Si-OH, and rheological data shows that product contains long-chain branch.In summary characterize data can be demonstrate,proved
It is bright that we obtain is the catenne shape polysiloxanes with long branched chain structure.In addition, thermogravimetic analysis (TGA) as shown by data we obtain
Product there is excellent heat endurance.
The present invention proposes a kind of new method of catenne shape polysiloxanes synthesis, and its advantage is：With reaction condition
Gently, applied widely, the advantages that energy consumption is low, combined coefficient is high, raw material is cheap and easy to get, product purification process is simple and easy, production
Thing has the advantages that superior heat-stability.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of methyl ethylene catenne shape polysiloxanes in embodiment 1；
Fig. 2 is that the hydrogen of methyl ethylene catenne shape polysiloxanes in embodiment 1 composes nuclear magnetic resonance figures；
Fig. 3 is that the silicon of methyl ethylene catenne shape polysiloxanes in embodiment 1 composes nuclear magnetic resonance figures；
Fig. 4 is methyl ethylene catenne shape polysiloxanes and the gel infiltration color before methyl silicate reaction in embodiment 1
Spectrogram；
Fig. 5 is methyl ethylene catenne shape polysiloxanes and the reacted gel infiltration color of methyl silicate in embodiment 1
Spectrogram；
Fig. 6 is the Cole-Cole figures of methyl ethylene catenne shape polysiloxanes in embodiment 1；
Fig. 7 is the hot weightless picture of methyl ethylene catenne shape polysiloxanes in embodiment 1.
Embodiment
The present invention is described in further detail below by embodiment, it is raw materials used commercially available in embodiment.
Embodiment 1：The preparation of methyl ethylene catenne shape polysiloxanes
- 75 DEG C, 0.15 gram of water is added to equipped with 150 gram 1,3,5- trimethyls -1,3,5- trivinyls cyclotrisiloxane,
In 1000 milliliters of three-necked flasks of 0.015 gram of Raney Ni and 500 milliliters of ether, stirring reaction adds 300 grams of activity after 10 minutes
Charcoal, stir 30 minutes, adsorbed, filter and pass through vacuum drying, obtain colourless viscous liquid, i.e. methyl ethylene catenne shape
Polysiloxanes, yield 80%, the weight average molecular weight of product is 8 × 105Dalton, molecular weight distribution 1.5.
The infrared spectrogram of methyl ethylene catenne shape polysiloxanes is as shown in figure 1, the poly- silica of methyl ethylene catenne shape
The hydrogen spectrum nuclear magnetic resonance figures of alkane is as shown in Fig. 2 silicon spectrum nuclear magnetic resonance figures such as Fig. 3 institutes of methyl ethylene catenne shape polysiloxanes
Show, methyl ethylene catenne shape polysiloxanes is with the gel permeation chromatography figure before methyl silicate reaction as shown in figure 4, methyl second
Alkenyl catenne shape polysiloxanes is with the reacted gel permeation chromatography figure of methyl silicate as shown in figure 5, methyl ethylene catenne
The Cole-Cole of shape polysiloxanes is schemed as shown in fig. 6, the hot weightless picture of methyl ethylene catenne shape polysiloxanes is as shown in Figure 7.
Embodiment 2：The preparation of methyl catenne shape polysiloxanes
- 5 DEG C, 8 grams of water are added to equipped with 240 grams of octamethylcy-clotetrasiloxanes, 2 grams of di-iron trioxides and 600 milliliters of tetrahydrochysenes
In 1000 milliliters of three-necked flasks of furans, stirring reaction is adsorbed after 4 hours, is filtered and is passed through vacuum drying, obtains colourless
Thick liquid, i.e. methyl catenne shape polysiloxanes, yield 90%, the weight average molecular weight of product is 6 × 106Dalton, molecular weight
It is distributed as 1.2.
Embodiment 3：The preparation of methyl hydrogen catenne shape polysiloxanes
30 DEG C, 30 grams of water are added to equipped with 300 gram 1,3,5,7,9- pentamethyl D5s, 7 grams of ferrocene and 500 are in the least
In 1000 milliliters of three-necked flasks for rising hexamethylene, stirring reaction adds 30 grams of activated carbons after 8 hours, stirs 15 minutes, is inhaled
It is attached, filtering, methanol is poured into after reaction solution is concentrated, obtains colourless viscous liquid, i.e. methyl hydrogen catenne shape polysiloxanes, yield
75%, the weight average molecular weight of product is 5 × 104Dalton, molecular weight distribution 1.7.
Embodiment 4：The preparation of aminomethyl phenyl catenne shape polysiloxanes
70 DEG C, 5 grams of water are added to equipped with 25 gram 1,3,5,7,9- pentamethyls -1,3, the siloxanes of 5,7,9- five benzyl ring five,
In 300 milliliters of three-necked flasks of 1.3 grams of ferric trichlorides and 100 milliliters of ethyl acetate, stirring reaction adds 5 grams of work after 10 hours
Property charcoal, stir 10 minutes, filter simultaneously precipitated with ethanol, obtain white solid, i.e. aminomethyl phenyl catenne shape polysiloxanes, produce
Rate 60%, the weight average molecular weight of product is 3 × 105Dalton, molecular weight distribution 1.3.
Embodiment 5：The preparation of phenyl epoxy radicals catenne shape polysiloxanes
90 DEG C, 24 grams of water are added to equipped with 40 grams of octaphenylcyclotetrasiloxanes, 20 grams of octa-epoxy cyclotetrasiloxanes, 4.8
In 300 milliliters of three-necked flasks of gram palladium bichloride and 100 milliliters of methyl iso-butyl ketone (MIBK)s, stirring reaction adds 15 grams of work after 12 hours
Property charcoal, stir 50 minutes, adsorbed, filter and pass through vacuum drying, obtain white solid, be i.e. phenyl epoxy radicals catenne shape gathers
Siloxanes, yield 75%, the weight average molecular weight of product is 8 × 104Dalton, molecular weight distribution 1.2.
Embodiment 6：The preparation of vinyl epoxy base catenne shape polysiloxanes
110 DEG C, 60 grams of water are added to equipped with 100 gram 1,3,5,7- tetravinyls -1,3, the silica of 5,7- tetra- epoxy radicals ring four
In 500 milliliters of three-necked flasks of alkane, 10 gram of six hydration chloroplatinic acid and 300 milliliters of ethyl acetate, stirring reaction is carried out after 20 hours
Absorption, reaction solution is poured into 300 ml methanols, is filtered and is passed through vacuum drying, obtains white solid, i.e. vinyl epoxy base
Catenne shape polysiloxanes, yield 85%, the weight average molecular weight of product is 6 × 106Dalton, molecular weight distribution 1.9.
Embodiment 7：The preparation of pi-allyl p- chloromethyl phenyl catenne shape polysiloxanes
140 DEG C, 56 grams of water are added to equipped with 70 gram 1,3,5,7- tetraallyls -1,3,5,7- tetra- (p- chloromethyl phenyls) rings
In 500 milliliters of three-necked flasks of tetrasiloxane, 0.1 gram of nickel acetylacetonate and 300 milliliters of methyl iso-butyl ketone (MIBK)s, stirring reaction 24 is small
Shi Hou, adsorbed, reaction solution is poured into 600 ml methanols, filtered and pass through vacuum drying, obtain white solid, i.e. alkene
Propyl group p- chloromethyl phenyl catenne shape polysiloxanes, yield 83%, the weight average molecular weight of product is 7 × 105Dalton, molecular weight
It is distributed as 1.7.
Embodiment 8：The preparation of n-butyl ethoxycarbonyl catenne shape polysiloxanes
100 DEG C, 9 grams of water are added to equipped with 9 gram 1,3,5,7- tetra-n-butyls -1,3, the silicon of 5,7- tetrapropylene acetoacetic ester basic ring four
In 100 milliliters of three-necked flasks of oxygen alkane, 0.5 gram of di-iron trioxide and 50 milliliters of ether, stirring reaction adds 0.5 after 17 hours
Gram activated carbon, stir 30 minutes, adsorbed, filter and pass through vacuum drying, obtain colourless liquid, i.e. n-butyl second
Ester group catenne shape polysiloxanes, yield 78%, the weight average molecular weight of product is 4 × 104Dalton, molecular weight distribution 1.4.
Embodiment 9：The preparation of cyclohexylacrylic ethoxycarbonyl catenne shape polysiloxanes
10 DEG C, 0.018 gram of water is added to equipped with 2 gram of eight cyclohexyl ring tetrasiloxane, 2 gram of eight silicon of ethyl acrylate basic ring four
In 300 milliliters of three-necked flasks of oxygen alkane, 0.01 gram of rhodium sesquioxide and 100 milliliters of butanone, stirring reaction adds 5 after 13 hours
Gram activated carbon, stir 20 minutes, adsorbed, filter, and pass through vacuum drying, obtain white solid, i.e. cyclohexylacrylic
Ethoxycarbonyl catenne shape polysiloxanes, yield 81%, the weight average molecular weight of product is 7 × 106Dalton, molecular weight distribution 1.3.
Claims (9)
1. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：- 75 DEG C, by 0.15
Gram water is added to equipped with 150 gram 1,3,5- trimethyls -1,3,5- trivinyls cyclotrisiloxane, 0.015 gram of Raney Ni and 500 milliliters
In 1000 milliliters of three-necked flasks of ether, stirring reaction adds 300 grams of activated carbons after 10 minutes, stirs 30 minutes, is inhaled
It is attached, filter and pass through vacuum drying, obtain colourless viscous liquid, i.e. methyl ethylene catenne shape polysiloxanes.
2. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：- 5 DEG C, by 8 grams of water
It is added to 1000 milliliters of three mouthfuls of burnings equipped with 240 grams of octamethylcy-clotetrasiloxanes, 2 grams of di-iron trioxides and 600 milliliters of tetrahydrofurans
In bottle, stirring reaction is adsorbed after 4 hours, is filtered and is passed through vacuum drying, obtains colourless viscous liquid, i.e. methyl catenne
Shape polysiloxanes.
3. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：30 DEG C, by 30 grams
Water is added to equipped with 300 gram 1,3,5,7,9- pentamethyl D5s, 1000 milliliters of 7 grams of ferrocene and 500 milliliters of hexamethylenes
In three-necked flask, stirring reaction adds 30 grams of activated carbons after 8 hours, stirs 15 minutes, is adsorbed, and filters, and reaction solution is dense
Methanol is poured into after contracting, obtains colourless viscous liquid, i.e. methyl hydrogen catenne shape polysiloxanes.
4. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：70 DEG C, by 5 grams of water
It is added to equipped with 25 gram 1,3,5,7,9- pentamethyls -1,3, the siloxanes of 5,7,9- five benzyl ring five, 1.3 grams of ferric trichlorides and 100 are in the least
In 300 milliliters of three-necked flasks for rising ethyl acetate, stirring reaction adds 5 grams of activated carbons after 10 hours, stirs 10 minutes, filtering
And precipitated with ethanol, obtain white solid, i.e. aminomethyl phenyl catenne shape polysiloxanes.
5. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：90 DEG C, by 24 grams
Water is added to equipped with 40 grams of octaphenylcyclotetrasiloxanes, 20 grams of octa-epoxy cyclotetrasiloxanes, 4.8 grams of palladium bichlorides and 100 milliliters of first
In 300 milliliters of three-necked flasks of base isobutyl ketone, stirring reaction adds 15 grams of activated carbons after 12 hours, stirs 50 minutes, carries out
Absorption, filter and pass through vacuum drying, obtain white solid, i.e. phenyl epoxy radicals catenne shape polysiloxanes.
6. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：110 DEG C, by 60 grams
Water is added to equipped with 100 gram 1,3,5,7- tetravinyls -1,3,5,7- tetra- epoxy radicals cyclotetrasiloxanes, 10 gram of six hydration chloroplatinic acid with
In 500 milliliters of three-necked flasks of 300 milliliters of ethyl acetate, stirring reaction is adsorbed after 20 hours, and reaction solution is poured into 300
In ml methanol, filter and pass through vacuum drying, obtain white solid, i.e. vinyl epoxy base catenne shape polysiloxanes.
7. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：140 DEG C, by 56 grams
Water is added to equipped with 70 grams of 1,3,5,7- tetraallyls -1,3,5,7- four（p- chloromethyl phenyl）Cyclotetrasiloxane, 0.1 gram
In 500 milliliters of three-necked flasks of nickel acetylacetonate and 300 milliliters of methyl iso-butyl ketone (MIBK)s, stirring reaction is adsorbed after 24 hours,
Reaction solution is poured into 600 ml methanols, filters and passes through vacuum drying, obtain white solid, i.e. pi-allylp- chloromethylbenzene
Base catenne shape polysiloxanes.
8. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：100 DEG C, by 9 grams
Water be added to equipped with 9 grams of 1,3,5,7- tetra-n-butyl -1,3,5,7- tetrapropylene acetoacetic ester basic rings tetrasiloxanes, 0.5 gram three
In 100 milliliters of three-necked flasks for aoxidizing two iron and 50 milliliters of ether, stirring reaction adds 0.5 gram of activated carbon, stirring after 17 hours
30 minutes, adsorbed, filter and pass through vacuum drying, obtain colourless liquid, be i.e. n-butyl ethoxycarbonyl catenne shape gathers
Siloxanes.
9. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：10 DEG C, by 0.018
Gram water is added to equipped with 2 gram of eight cyclohexyl ring tetrasiloxane, 2 gram of eight ethyl acrylate basic ring tetrasiloxane, 0.01 gram of three oxidation two
In 300 milliliters of three-necked flasks of rhodium and 100 milliliters of butanone, stirring reaction adds 5 grams of activated carbons after 13 hours, stirs 20 minutes,
Adsorbed, filtered, and pass through vacuum drying, obtain white solid, i.e. cyclohexylacrylic ethoxycarbonyl catenne shape polysiloxanes.
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