CN1206019A - Tubular organosilicon polymer and its preparation and application - Google Patents
Tubular organosilicon polymer and its preparation and application Download PDFInfo
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- CN1206019A CN1206019A CN 97112236 CN97112236A CN1206019A CN 1206019 A CN1206019 A CN 1206019A CN 97112236 CN97112236 CN 97112236 CN 97112236 A CN97112236 A CN 97112236A CN 1206019 A CN1206019 A CN 1206019A
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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
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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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
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
Abstract
The tubular organosilicon polymer is prepared through the reaction of ladder orgnosilicon polymer with or without active reaction group and proper coupling agent. It can dissolve in various organic solvent and has nanometer level pores and regular structure, and its molecular pore size and chemical affinity can be regulated through selection of the ladder polymer and coupling agent. Its molecular weight range is 10 to the power 3-10 to the power 6. It can form several kinds of compounds in conjunction with molecule with proper size and chemical affinity, and the compounds has wide application in molecular device, nanometer reactor, and catalysis, separation and other field related to molecule recognition.
Description
The present invention relates to a kind of novel organosilicon macromolecule, particularly a kind of tubular organosilicon polymer with tubular structure.
Known polymkeric substance with tubular structure, such as, S.Iijima rolled up at Nature the 354th in 1991, the 56th page of preparation and the structure of having reported carbon nanotube, and it is a kind of inorganic nanotube.People such as AkiraHarada has reported the tubular structure that obtains with the polymerization of natural matter cyclodextrin in recent years.Because the unitary size and dimension of cyclodextrin etc. be certain, also be certain by the aperture and the affinity of the tracheary element of its gained, be difficult to adjusting.People such as nineteen ninety-five H.Nakamura have reported the tubular high polymer that forms with silicone gel, are the insoluble polymer that does not melt.For above-mentioned reasons, influenced being extensive use of of they.July nineteen ninety-five application number be 941005071 patent disclosure " trapezoidal polyhydric sesquisiloxane of high-regularity and multipolymer thereof and their method for making ".January nineteen ninety-five, patent JP08188649 disclosed " high-regularity contains trapezoidal polysilsesquioxane and the multipolymer and their method for making of active reaction base ".They are from containing the organosilane monomer of active group: trichlorosilane, vinyl trichloro silane, the propenyl trichlorosilane, oxyethyl group silicofluoroform etc. sets out, with α, ω-diamines is a coupling agent, the ladderlike polymer of the high-regularity that the method by pre-coupling and progressively hydrolysis, condensation makes, and structural formula is:
Poly-trapezoidal silsesquioxane polymer (abbreviating R-T as) structural formula (R, R ＇ is respectively identical vinyl, propenyl, hydrogen, alkoxyl group, or the like, also can be respectively different above-mentioned groups).This is double-stranded ladderlike polymer, does not present the tracheary element structure.The present invention has overcome the deficiency of the cross-linking system that mineral-type molecule in the above-mentioned example or natural molecule polymkeric substance maybe can not dissolve, a kind of synthesizing organo-silicon tubular high polymer method is provided, can be more easily selection and choice of Solvent by the coupling agent size, affinity and the molecular conformation that change molecule.Its solubility is shaped to the reprocessing of system convenience also is provided.The present invention is a raw material with above-mentioned organosilicon ladderlike polymer, with the further coupling of its side group that can react, thereby provides a kind of microtexture (comprising caliber size and chemical affinity) controlled tubulose solubility organosilicon macromolecule; The structural formula of this tubular high polymer such as Fig. 1.
Fig. 1 a is two and contains and react to each other between the trapezoidal molecule of functional group not of the same race and coupling forms tubular structure, as Ally-T and H-T, Vi-T and H-T, H-T and EtO-T etc., or be two to contain between the functional group's of the same race trapezoidal molecule and form tubular high polymer by the coupling agent coupling, as Vi-T and Vi-T, Ally-T and Ally-T, EtO-T EtO-T and between coupling by coupling agent.
But Fig. 1 b is the reactive behavior base on the same trapezoidal molecular backbone chain forms tubular high polymer by the coupling agent coupling.
Or
For connecting the abutment of trapezoidal main chain, described abutment is: (CH
2)
x, CH
2CH
2(SiMe
2O)
xCH
2CH
2, CH
2(CH
2)
mC
6H
4(CH
2)
mCH
2, CH
2(CH
2)
nOC
6H
4O (CH
2)
nCH
2, O (CH
2)
nC
6H
4(CH
2)
nO, or OOC (CH
2)
nC
6H
4(CH
2)
nCOO, x=2-10 in the formula, m=1-10, n=0-10.
The preparation method of tubular high polymer
The preparation method of tubular high polymer of the present invention carries out according to the following steps: one, the organosilicon ladderlike polymer of the band reactive behavior base of synthetic high-regularity, two, introduce trapezoidal exposed terminated groups fixing agent and template, three, form the tubular polymer of solubility through linked reaction.
One, the organosilicon ladderlike polymer of the band reactive behavior base of synthetic high-regularity:
1) Vi-T's is synthetic
In reactor, add vinyl trichloro silane and dry toluene (concentration range is the 0.05-0.2 grams per milliliter), keep to bathe temperature and be-20-0 ℃, add the anhydrous propanone solution (concentration range is the 0.02-0.1 grams per milliliter) of Ursol D, stirred 0.5-1 hour.The mol ratio of trichloromethane and Ursol D is then to add with dry acetone dilute aqueous (concentration be 0.02-0.1 ml water/milliliter acetone) 25 ℃ stirrings 1-2 hour at 1: 1, and the mol ratio of water and vinyl trichloro silane is 1.5-3: 1.With the ammonium salt elimination, filtrate water is washed neutral and is used anhydrous sodium sulfate drying then.
2) Ally-T's is synthetic
In reactor, add propenyl trichlorosilane and dry toluene (concentration range is the 0.05-0.2 grams per milliliter), keep to bathe temperature and be-20-0 ℃, add the anhydrous propanone solution (concentration range is the 0.02-0.1 grams per milliliter) of Ursol D, stirred 0.5-1 hour.The mol ratio of propenyl trichloromethane and Ursol D is 1: 1.Add with dry acetone dilute aqueous (concentration is 0.02-0.1 ml water/milliliter acetone) then.When adding the aqueous solution, add quantitative pyridine.The mol ratio of water and propenyl trichlorosilane is 1.5-3: 1.The mol ratio of pyridine and propenyl trichlorosilane is 1-2: 1.25 ℃ were stirred 1-2 hour, and then with the ammonium salt elimination, filtrate water is washed neutral and used anhydrous sodium sulfate drying.
3) H-T's is synthetic
Add trichlorosilane and dry toluene (concentration range is the 0.05-0.1 grams per milliliter) in reactor, keep bathing temperature and be-30-0 ℃, the anhydrous propanone solution (concentration range is the 0.02-0.1 grams per milliliter) of adding Ursol D stirred 0.5-1 hour.The mol ratio of trichlorosilane and Ursol D is 1: 1.Add with dry acetone dilute aqueous (concentration is 0.02-0.1 ml water/milliliter acetone) then, the mol ratio of trichlorosilane and water is 1: 1-5.25 ℃ were stirred 1-2 hour, and then with the ammonium salt elimination, filtrate water is washed neutral and used anhydrous sodium sulfate drying.
4) EtO-T's is synthetic
In reactor, add oxyethyl group trichlorosilane and dry toluene (concentration range is the 0.05-0.1 grams per milliliter), keeping bathing temperature is subzero 30 ℃ to 0 ℃, add the anhydrous propanone solution (concentration range is the 0.02-0.1 grams per milliliter) of Ursol D, stirred 0.5-1 hour.The mol ratio of oxyethyl group trichlorosilane and Ursol D is 1: 1.Add dry acetone dilute aqueous (concentration is 0.02-0.1 ml water/milliliter acetone) then, the mol ratio of oxyethyl group trichlorosilane and water is 1: 1-5 adds quantitative pyridine when adding the aqueous solution.The mol ratio of pyridine and oxyethyl group trichlorosilane is 1-2: 1,25 ℃ was stirred 1-2 hour, and then with the ammonium salt elimination, filtrate water is washed neutral and used anhydrous sodium sulfate drying.
Two, introduce trapezoidal molecular chain-end fixing agent and template
The strong end of trapezoidal molecule fixing agent be can with the molecule of two functional groups of trapezoidal molecular end hydroxyl reaction, as HO-[Si (CH
3)
2O-]
m-OH (m=1-10), HO (CH
2)
xOH (x=2-10), Resorcinol etc., the template of introducing can produce the molecule of hydrogen bond action with ladderlike polymer for (1).(2) can partly introduce electron rich group and electron deficiency group in the trapezoidal molecule.(3) can form the ion of complex compound with trapezoidal molecule coordination.
Three, by the controlled tubular organosilicon polymer of linked reaction composite structure
Above-mentioned linked reaction has three kinds: 1, addition reaction of silicon with hydrogen, 2, the silicon oxidation reactions of hydrocarbons, 3, the reaction of silicon acyloxylation
1, addition reaction of silicon with hydrogen:
This addition reaction of silicon with hydrogen is the addition reaction of silicon hydride and unsaturated hydro carbons.The side group of ladderlike polymer is a vinyl, propenyl, hydrogen, tubular high polymer is synthesized in the coupling of available silicon addition reaction of hydrogen.Ladderlike polymer in following three kinds of modes by coupling: (table 1)
(1) contain the coupling that reacts to each other between functional group's two trapezoidal molecules not of the same race, as Ally-T and H-T, Vi-T and H-T etc.Synthesis step is as follows: two kinds of ladderlike polymers are dissolved in exsiccant respectively hold in the agent; mol ratio by 1: 0.8 to 1: 1.5 under protection of inert gas adds in the reactor; and adding solvent and corresponding catalyzer, reactant concn is every milliliter of a 10-40 milligram.Reacted 12-72 hour down at 50-120 ℃.Removing desolvates obtains product.The structural formula of the tubular high polymer that forms is Fig. 1 a.
(2) contain between two trapezoidal molecules of functional group of the same race coupling by coupling agent, as Vi-T and Vi-T, Ally-T and Ally-T, the coupling by coupling agent between H-T and the H-T etc.Synthesis step is as follows: two kinds of ladderlike polymers are dissolved in respectively in the exsiccant solvent, add in the reactor under protection of inert gas, and add solvent and corresponding catalyzer, coupling agent, reactant concn is every milliliter of a 10-40 milligram.Reacted 12-72 hour down at 30-100 ℃.Removing desolvates obtains product.The structural formula of the tubular high polymer that forms is Fig. 1 a.
(3) but the coupling of the reactive behavior base on the same trapezoidal molecular backbone chain by coupling agent.As: H-T, Vi-T, a ladderlike polymer self such as Alltl-T side group is by the coupling of coupling agent.Synthesis step is as follows: ladderlike polymer is dissolved in the exsiccant solvent, adds in the reactor under protection of inert gas, and add solvent, catalyzer and coupling agent, reactant concn is every milliliter of a 5-10 milligram.Reacted 12-72 hour down at 30-100 ℃.Removing desolvates obtains product.The structural formula of the tubular high polymer that forms comprises for the solvent of the above-mentioned addition reaction of silicon with hydrogen of Fig. 1 b: toluene, dimethylbenzene, glycol dimethyl ether, allyl polyether, dimethyl phthalate, tetrahydrofuran (THF), 1,4-dioxane, pimelinketone, acetone, alcohols equal solvent or its mixed solvent.Solvent load is corresponding every gram R-T with 50 milliliters to 500 milliliters solvents.
Above-mentioned silicon hydrogen addition coupling agent comprises: H-[Si (CH
3)
2O-]
x-H (x=2-10), 1,4-divinylbenzene, 1,4-diallyl dihydroxy-benzene ether, CH
2=CH-(CH
2)
n-CH=CH
2(n=0-10) or CH
2=CH-[Si (CH
3)
2O-]
x-CH=CH
2(x=2-10) etc.The mol ratio of coupling agent and R-T is 1.5-0.8: 1.
The catalyzer of the addition reaction of silicon with hydrogen that the present invention relates to can be to the effective various catalyzer of silicon H-H reaction addition, the transition metal complex catalysts that addition has highly selective to silicon hydrogen especially, as: the catalyzer H of platinum
2PtCl
66H
2O, Cp
2PtCl
2, Pt and Vi-SiMe
2OSiMe
2The complex compound of-Vi (Karstedt ' s catalyzer), and Pt
0-1VComplex compound with vinyl compound; The complex compound of palladium and rhodium, and these metal chelate and metallic colloid catalyzer etc.Catalyst consumption is 0.5ppm-1%.
2, silicon oxidation reactions of hydrocarbons:
This silicon oxidation reactions of hydrocarbons is silicon hydrogen, silicon oxyethyl group or is transformed silicon hydroxyl and dehydration, the dehydrogenation of dibasic alcohol, dihydric phenol and binary silanol or the reaction of sloughing ethanol generation silane (virtue) oxygen base that get by silicon hydrogen, silicon oxyethyl group.
This type of reaction is applicable to that reactive group is a hydrogen, the ladderlike polymer of alkoxyl group.
Ladderlike polymer in following three kinds of modes by coupling: (table 1)
(1) contains the coupling that reacts to each other between two trapezoidal molecules of functional group of the same race not; as EtO-T and H-T; synthesis step is as follows: two kinds of ladderlike polymers are dissolved in respectively in the exsiccant solvent; mol ratio by 1: 0.8 to 1: 1.5 under protection of inert gas adds in the reactor; and adding solvent and corresponding catalyzer, reactant concn is every milliliter of a 10-40 milligram.Reacted 12-72 hour down at 50-120 ℃, remove the small molecules that dereaction generates simultaneously, removing desolvates obtains product.The structural formula of the tubular high polymer that forms is Fig. 1 a.
(2) contain between two trapezoidal molecules of functional group of the same race coupling by coupling agent, as EtO-T and EtO-T, the coupling by coupling agent between H-T and the H-T.Synthesis step is as follows: two kinds of ladderlike polymers are dissolved in respectively in the exsiccant solvent, add in the reactor under protection of inert gas, and add solvent and corresponding catalyzer and coupling agent, every milliliter of reactant concn 10-40 milligram.Reacted 12-72 hour down at 30-100 ℃.Remove the small molecules that dereaction generates simultaneously, removing desolvates obtains product.The structural formula of the tubular high polymer that forms is Fig. 1 a.
(3) but contain the coupling of reactive behavior base by coupling agent on the functional group's of the same race same trapezoidal molecular backbone chain.As EtO-T or H-T, ladderlike polymer self side group is by the coupling of coupling agent.Synthesis step is as follows: ladderlike polymer is dissolved in the exsiccant solvent, adds in the reactor under protection of inert gas, and add catalyzer and coupling agent, reactant concn is every milliliter of a 5-10 milligram.Reacted 12-72 hour down at 30-100 ℃.Remove the small molecules that dereaction generates simultaneously, the structural formula that obtains the tubular high polymer of product formation except that desolvating is Fig. 1 b.
The agent of the employed hydrocarbon oxidative coupling of above-mentioned silicon oxidation reactions of hydrocarbons comprises: HO-[Si (CH
3)
2O-]
x-OH (x=2-10), HO (CH
2)
xOH (x=2-10), Resorcinol, bisphenol-A, to two benzylalcohols, and their an alkali metal salt etc.The consumption of coupling agent is 1.5-0.8 a times of R-T mole number.
The solvent of the linked reaction that above-mentioned silicon oxidation reactions of hydrocarbons is related is except that alcoholic solvent is restricted to the mixed solvent of low-boiling point alcohol, and is identical with the addition reaction of silicon with hydrogen solvent for use.
The catalyzer that above-mentioned silicon oxidation reactions of hydrocarbons relates to is alkali-metal oxide compound, oxyhydroxide, sodium alkoxide, phenol sodium, mineral acid, strong organic acid, halogenide, amine etc.Catalyst consumption is thousandth to ten/one.
3, silicon acyloxylation reaction:
The reaction of this silicon acyloxylation is for the silicon oxyethyl group or have silicon hydroxyl that silicon oxyethyl group, the hydrolysis of silicon hydrogen get and di-carboxylic acid or acyl chloride reaction to slough acetate or hydrogenchloride, the reaction of generation silicon acyloxy.This type of reaction is applicable to that reactive group is a hydrogen, the ladderlike polymer of alkoxyl group.
Ladderlike polymer in following three kinds of modes by coupling: (table 1)
(1) two contains the coupling that reacts to each other between the trapezoidal molecule of functional group not of the same race; as EtO-T and H-T; synthesis step is as follows: two kinds of ladderlike polymers are dissolved in respectively in the exsiccant solvent; mol ratio by 1: 0.8 to 1: 1.5 under protection of inert gas adds in the reactor; and adding solvent and corresponding catalyzer, reactant concn is every milliliter of a 10-40 milligram.Reacted 12-72 hour down at 50-120 ℃.Remove the small molecules that dereaction generates simultaneously, removing desolvates obtains product.The structural formula of the tubular high polymer that forms is Fig. 1 a.
(2) two contain between the functional group's of the same race trapezoidal molecule coupling by coupling agent, as EtO-T and EtO-T.Coupling by coupling agent between H-T and the H-T.Synthesis step is as follows: two kinds of ladderlike polymers are dissolved in respectively in the exsiccant solvent, under protection of inert gas, add in the reactor, and add corresponding catalyzer and coupling agent, reactant concn is every milliliter of a 10-40 milligram.Reacted 12-72 hour down at 30-100 ℃.Remove the small molecules that dereaction generates simultaneously, removing desolvates obtains product.The structural formula of the tubular high polymer that forms is Fig. 1 a.
(3) but contain the coupling of reactive behavior base by coupling agent on the functional group's of the same race same trapezoidal molecular backbone chain.H-T or a ladderlike polymer self of EtO-T side group are by the coupling of coupling agent.Synthesis step is as follows: ladderlike polymer is dissolved in the exsiccant solvent, adds in the reactor under protection of inert gas, and add catalyzer and coupling agent, reactant concn is every milliliter of a 5-10 milligram.Reacted 12-72 hour down at 30-100 ℃.Remove the small molecules that dereaction generates simultaneously, removing desolvates obtains product.The structural formula of the tubular high polymer that forms is Fig. 1 b.
This silicon acyloxylation is reacted employed coupling agent and is comprised: HOOC (CH
2)
mCOOH (m=1-10), HOOC (C
6H
4)
yCOOH (y=1-2), XOC (CH
2)
nCOX (n=0-10), XOC (C
6H
4)
yCOX (y=1-2), the X=halogen, etc.The consumption of coupling agent is 1.5-0.8 a times of R-T mole number.
The related reaction solvent of this silicon acyloxylation reaction is except that alcohols is inapplicable, and is identical with the addition reaction of silicon with hydrogen solvent for use.
The catalyzer that this silicon acyloxylation reaction relates to can be strong mineral acid, aluminium, iodine, or the transition metal of colloid nickel and group VIII and its complex compound etc.Catalyst consumption is thousandth to ten/one.
Tubular organosilicon polymer of the present invention has microscopic dimensions and affinity can obtain suitable control (table 1)
Table 1
*The AFM data be observe be divided into higher part than highlights.Molecule is orderly stripe-arrangement in the AFM photo.Listed data are the bright wisp spacing in the table, from the width that to a certain degree reflected molecular chain but more smaller than developed width.
From DSC, the data of scattering of light see that resulting tubular high polymer is club shaped structure and has certain rigid.
The gained tubular high polymer can dissolve in organic solvent simultaneously, helps these solvents of further processing treatment and comprises: toluene, dimethylbenzene, glycol dimethyl ether, allyl polyether, dimethyl phthalate, tetrahydrofuran (THF), 1, the 4-dioxane, pimelinketone, acetone, Virahol, isopropylcarbinol equal solvent or its mixed solvent.
And this novel tubular polymer can form mixture with guest molecule, have broad application prospects according to its special construction and Adjustable structure joint property, can construct advanced functional material, as: biosensor, the supramolecule catalyzer, the supramolecule separatory membrane, novel optical material and tables 1 such as novel electricity material: different tubular high polymer calibers and sign
| Mode | Become the tube reaction type | Size () | Characterize | |
| Internal diameter molecular simulation value | External diameter molecular simulation value/AFM value | |||
| ??I | React coupling between A.H-T and Vi-T | 1～2 | ?6～9/6.5 | 2240cm in the IR spectrogram of tubular organosilicon polymer -1And 1600cm -1The silicon hydrogen and the peak of silico ethylene and propenyl disappear, 1H- NMR 13C-NMR 29The peak of Si-H and Vi-Si disappears substantially among the Si-NMR; The corresponding value of 2 θ peakedness ratio ladderlike polymer precursors of X-ray diffraction reduces. and be that long-range order increases. |
| React coupling between B.H-T and Allyl-T | 2～3 | ?8～12/8.2 | ||
| ??Ⅱ | Pass through the Vi-MM coupling between A.H-T; Pass through the H-MM coupling between B.Vi-T | 5～9 | ?10～15/10 | |
| Pass through the Allyl-MM coupling between C.H-T; Pass through the H-MM coupling between D.Allyl-T; | 5～10 | ?12～16/10.3～10.9 | ||
| Pass through two benzylalcohol couplings between E.EtO-T | 5～8 | ?10～12/8.5 ? | The peak of visible raw material oxyethyl group and hydroxyl significantly reduces from the IR﹠H-NMR spectrogram. from the IR spectrogram, and 2280cm -1And 1600cm -1 | |
| ??Ⅲ??? | Pass through the H-MM coupling between A. same Vi-T molecular chain; | 1～2 | ?6～9/6.5 | Silicon hydrogen silico ethylene base, the peak of silicon propenyl disappears. 1H-NMR? 13C-NMR 29The peak of Si-H and Vi-T disappears substantially among the Si-NMR. |
| Pass through the H-MM coupling between B. same Allvl-T molecular chain; | 2～3 | ?8～12/9.3 | ||
| Pass through the Vi-MM coupling between C. same H-T molecular chain | 1～2 | ?6～9/6.5 | ||
| Pass through HO (CH between D. same EtO-T molecular chain 2) 4C 6H 4(CH 2) 4The OH coupling | 4～7 | ?8～11/9.5 | From IR﹠ 1The peak of visible raw material oxyethyl group and hydroxyl significantly reduces in the H-NMR spectrogram. | |
Embodiment
Pass through the HMM coupling between 1: two Vi-T of embodiment
In 500 milliliters three-necked bottle, it is good to put into magnetic agitation, vacuumizes, then applying argon gas.Repeatable operation three times.Under argon shield, add 100 milliliters of THF solvents with syringe, the Vi-T (toluene solution of 40mg/ml) and 1,1,3 of 1.5 grams, 3-tetramethyl disiloxane (HMM is mixed with the 1ml/25ml tetrahydrofuran solution) 1.28 grams.The Cp that adds 0.5 milligram
2PtCl
2Catalyzer was 70 ℃ of back flow reaction 48 hours.40 ℃ of following pressure reducing and steaming tetrahydrofuran (THF)s are removed residual solvent under 25 ℃, obtain white solid product.Product can redissolve in tetrahydrofuran (THF), 2280cm in the infrared spectrum
-1And 1600cm
-1Silicon hydrogen and the peak of silico ethylene base disappear substantially, show that reaction is more complete.Molecular simulation tubular polymer internal diameter is 5～9 , and external diameter is 10～15 .It is 10 that AFM tests its external diameter.
Pass through the HMM coupling between 2: two Ally-T of embodiment
In 500 milliliters three-necked bottle, it is good to put into magnetic agitation, vacuumizes, then applying argon gas.Repeatable operation three times.Under argon shield, add 100 milliliters of cyclohexanone solvents with syringe, toluene 100ml, the Allyl-T (toluene solution of 40mg/ml) and 1,1,3 of 1.76 grams, 3-tetramethyl disiloxane (HMM is mixed with the 1ml/25ml tetrahydrofuran solution) 1.28 grams.The Cp that adds 5 milligrams
2PtCl
2Catalyzer was 70 ℃ of back flow reaction 14 hours.The solvent of 40 ℃ of following pressure reducing and steaming 2/3rds is removed residual solvent under 25 ℃, obtains white solid product.Product can redissolve in pimelinketone, 2280cm in the infrared spectrum
-1And 1600cm
-1Silicon hydrogen and the peak of silicon propenyl disappear substantially, show that reaction is more complete.Molecular simulation tubular polymer internal diameter is 5～10 , and external diameter is 12～16 , and it is 10.9 that AFM tests its external diameter.
Pass through H (SiMe between 3: two Ally-T of embodiment
2O)
3The H coupling
In 500 milliliters three-necked bottle, it is good to put into magnetic agitation, vacuumizes, then applying argon gas.Repeatable operation three times.Under argon shield, add 100 milliliters of cyclohexanone solvents with syringe, toluene 100ml, the Allyl-T (toluene solution of 40mg/ml) and the H (SiMe of 1.86 grams
2O)
3H (being mixed with the 1ml/25ml tetrahydrofuran solution) 1.87 grams.The Cp that adds 5 milligrams
2PtCl
2Catalyzer was 70 ℃ of back flow reaction 14 hours.The solvent of 40 ℃ of following pressure reducing and steaming 2/3rds is removed residual solvent under 25 ℃, obtains white solid product.Product can redissolve in pimelinketone, 2280cm in the infrared spectrum
-1And 1600cm
-1Silicon hydrogen and the peak of silicon propenyl disappear substantially, show that reaction is more complete.
Pass through the addition reaction of silicon with hydrogen coupling between embodiment 4:H-T and the Vi-T
In 500 milliliters three-necked bottle, put into the magnetic agitation seed, vacuumize, then applying argon gas.Repeatable operation three times.Under argon shield; add 100 milliliters of tetrahydrofuran (THF)s with syringe, 100 milliliters of pimelinketone, the Vi-T (toluene solution of 40mg/ml) and 1.1 that adds 1.5 grams again restrains H-T (toluene solution of 10mg/ml); Karstedt ' s the catalyzer that adds 4 milligrams was 60 ℃ of back flow reaction 36 hours.40 ℃ of following pressure reducing and steaming tetrahydrofuran (THF)s and part pimelinketone are removed residual solvent under 25 ℃, obtain white solid product.Molecular simulation tubular polymer internal diameter is 1～2 , and external diameter is 6～9 .It is 6.5 that AFM tests its external diameter.
Pass through the addition reaction of silicon with hydrogen coupling between embodiment 5:H-T and the Allyl-T
In 500 milliliters three-necked bottle, put into the magnetic agitation seed, vacuumize, then applying argon gas.Repeatable operation three times.Under argon shield, add 100 milliliters of tetrahydrofuran (THF)s with syringe, 100 milliliters of pimelinketone, the Vi-T (toluene solution of 40mg/ml) and 1.1 that adds 1.7 grams again restrains H-T (toluene solution of 10mg/ml), adds 6 milligrams H
2PtCl
66H
2The O catalyzer was 70 ℃ of back flow reaction 48 hours.40 ℃ of following pressure reducing and steaming tetrahydrofuran (THF)s and part pimelinketone are removed residual solvent under 25 ℃, obtain white solid product.Molecular simulation tubular polymer internal diameter is 2～3 , and external diameter is 8～12 .It is 8.2 that AFM tests its external diameter.
Pass through the HMM coupling between the vinyl on 6: one Vi-T main chains of embodiment
In three-necked bottle, it is good to put into magnetic agitation, vacuumizes, then applying argon gas.Repeatable operation three times.Under argon shield, add 300 milliliters of THF solvents with syringe, dimethylbenzene 100ml, the Vi-T (toluene solution of 20mg/ml) and 1,1,3 of 1.5 grams, 3-tetramethyl disiloxane (HMM is mixed with the 1ml/25ml tetrahydrofuran solution) 1.28 grams.The Pt/C catalyzer that adds 5 milligrams was 70 ℃ of back flow reaction 36 hours.40 ℃ of following pressure reducing and steaming tetrahydrofuran (THF)s are removed residual solvent under 25 ℃, obtain white solid product.Product can redissolve in tetrahydrofuran (THF), 2280cm in the infrared spectrum
-1And 1600cm
-1Silicon hydrogen and the peak of silicon propenyl disappear substantially, show that reaction is more complete.Molecular simulation tubular polymer internal diameter is 1～2 , and external diameter is 6～9 .AFM test external diameter is 6.5 .
Pass through the HMM coupling between the propenyl on 7: one Allyl-T main chains of embodiment
In three-necked bottle, it is good to put into magnetic agitation, vacuumizes, then applying argon gas.Repeatable operation three times.Under argon shield, add 300 milliliters of THF solvents with syringe, dimethylbenzene 100ml, the Allyl-T (toluene solution of 40mg/ml) and 1,1,3 of 1.7 grams, 3-tetramethyl disiloxane (HMM is mixed with the 1ml/25ml tetrahydrofuran solution) 1.28 grams.The Cp that adds 5 milligrams
2PtCl
2Catalyzer was 60～70 ℃ of back flow reaction 36 hours.40 ℃ of following pressure reducing and steaming tetrahydrofuran (THF)s are removed residual solvent under 25 ℃, obtain white solid product.Product can redissolve in tetrahydrofuran (THF), 2280cm in the infrared spectrum
-1And 1600cm
-1Silicon hydrogen and the peak of silicon propenyl disappear substantially, show that reaction is more complete.Molecular simulation tubular polymer internal diameter is 2～3, and external diameter is 8～12 .AFM test external diameter is 9.3 .
Embodiment between H-T passes through Vi-MM coupling at 8: two
In 500 milliliters three-necked bottle, put into the magnetic agitation seed, vacuumize, then applying argon gas.Repeatable operation three times.Under the noble gas protection, pipette 300 milliliters of THF solvents with syringe, add 1,1,3,3-tetramethyl--1,3-divinyl disiloxane (Vi-MM is made into THF solution with it, and concentration is 0.04 mg/ml) 1.4 grams, H
2PtCl
66H
25 milligrams of O catalyzer add 0.81 milliliter of the toluene solution (solid content is 13.4mg/ml) of H-T at last.60～70 ℃ of reactions 36 hours.Obtain the film of a transparent homogeneous after the solvent evaporates, 2240cm in the infrared spectrum
-1And 1600cm
-1Silicon hydrogen and the peak of silico ethylene base disappear substantially, show that reaction is more complete.Molecular simulation tubular polymer internal diameter is 5～10 , and external diameter is 12～16 .It is 10.3 that AFM tests its external diameter.
Coupling between embodiment 9:H-T and the EtO-T
In 500 milliliters three-necked bottle, put into the magnetic agitation seed, vacuumize, then applying argon gas.Repeatable operation three times.Under argon shield, add THF50ml and glycol dimethyl ether 150ml with syringe, add EtO-T (30 mg/ml THF solution) 2 grams and H-T (15 mg/ml THF solution) 1 gram.The NaOH aqueous solution with 0.2ml 5% mixes adding with 20 milliliters of acetone again.25 ℃ were stirred 3 hours down.Heat up gradually, to there being solvent slowly to steam, back flow reaction also steamed the ethanol that reaction generates in 48 hours gradually again.Product washes with water neutral, except that after desolvating, washes for several times with methyl alcohol, and drying obtains final product.As can be seen, the peak of former oxyethyl group and silicon hydrogen has reduced more than 90% from infrared and proton magnetic spectrum figure, the peak of hydroxyl is also very weak, illustrates that most of oxyethyl group and silicon hydrogen are by coupling.
Side group on 10: one EtO-T main chains of embodiment is by the Resorcinol coupling.
In 1000 milliliters three-necked bottle, put into the magnetic agitation seed, vacuumize, then applying argon gas.Repeatable operation three times.Under argon shield, add toluene 250ml and glycol dimethyl ether 250ml adding EtO-T (30 mg/ml THF solution) 2 grams with syringe.Resorcinol 2 gram and 0.05 restrains is scattered in Resorcinol sodium in the 20ml THF solution, 50 ℃ slowly are added dropwise to system, wait to be added drop-wise to three/for the moment, heat up gradually, to there being solvent slowly to steam, continue to drip, after dropwising, back flow reaction also steamed the ethanol that reaction generates in 48 hours gradually again.Product is washed for several times with methyl alcohol after removing and desolvating, and drying obtains final product.As can be seen, the peak of former oxyethyl group has reduced 85% from infrared and proton magnetic spectrum figure, the peak of hydroxyl is also very weak, illustrates that most of oxyethyl group is by coupling.Molecular simulation tubular polymer internal diameter is 2～3 , and external diameter is 5～8 .AFM tests to such an extent that its external diameter is 7 .
Embodiment EtO-T between passes through two benzylalcohol couplings at 11: two.
In 500 milliliters three-necked bottle, put into the magnetic agitation seed, vacuumize, then applying argon gas.Repeatable operation three times.Under argon shield, add toluene 250ml with syringe, add EtO-T (30 mg/ml THF solution) 2 grams.Be scattered in Resorcinol sodium in the 20ml THF solution to what two benzylalcohols 2.4 gram and 0.1 restrained, 25 ℃ slowly are added dropwise to system, wait to be added drop-wise to three/for the moment, heat up gradually, to there being solvent slowly to steam, continue to drip, after dropwising, back flow reaction also steamed the ethanol that reaction generates in 48 hours gradually again.Product is washed for several times with methyl alcohol after removing and desolvating, and drying obtains final product.As can be seen, the peak of former oxyethyl group has reduced 80% from infrared and proton magnetic spectrum figure, the peak of hydroxyl is also very weak, illustrates that most of oxyethyl group has reacted, and two ladderlike polymers are by coupling.Molecular simulation tubular polymer internal diameter is 5～8 , and external diameter is 10～12 .AFM tests to such an extent that its external diameter is 9.5 .
Embodiment H-T between passes through HOOC (CH) at 12: two
4The COOH coupling.
In 500 milliliters three-necked bottle, put into the magnetic agitation seed, vacuumize, then applying argon gas.Repeatable operation three times.Under argon shield, add dimethylbenzene 200ml with syringe, add H-T (10 mg/ml THF solution) 2 grams.Add to 1 6-hexanodioic acid 2.6 gram and Cp again
2PtCl
20.02 gram, 30 ℃ slowly are added dropwise to system, wait to be added drop-wise to three/for the moment, are warming up to 60 ℃ gradually, continue to drip, and after dropwising, reflux 12 hours again.Product is washed for several times with methyl alcohol after removing and desolvating, and drying obtains final product.As can be seen, the peak of silicon hydrogen has reduced 90% from infrared and proton magnetic spectrum figure, the peak of hydroxyl is also very weak, illustrates that most of silicon hydrogen base is by coupling.
Embodiment 13: same H-T side group is by HOOC (CH
2)
4The COOH coupling.
In 1000 milliliters three-necked bottle, put into the magnetic agitation seed, vacuumize, then applying argon gas.Repeatable operation three times.Under argon shield, add dimethylbenzene 600ml with syringe, add H-T (10 mg/ml THF solution) 2 grams.Add to 1 6-hexanodioic acid 2.5 gram and Cp again
2PtCl
20.015 gram, 30 ℃ slowly are added dropwise to system, wait to be added drop-wise to three/for the moment, are warming up to 50 ℃ gradually, continue to drip, and after dropwising, reflux 12 hours again.Product is washed for several times with methyl alcohol after removing and desolvating, and drying obtains final product.As can be seen, the peak of silicon hydrogen has reduced 90% from infrared and proton magnetic spectrum figure, the peak of hydroxyl is also very weak, illustrates that most of silicon hydrogen base is by coupling.
Embodiment 14:H-T and EOt-T are by ClOC (C
6H
4) the COCl coupling
In 500 milliliters three-necked bottle, put into the magnetic agitation seed, vacuumize, then applying argon gas.Repeatable operation three times.Under argon shield, add dimethylbenzene 100ml and diethylene glycol dimethyl ether 100ml with syringe, add H-T (15 mg/ml THF solution) 1 gram and EtO-T1.8 gram.25 ℃ add ClOC (C
6H
4) COCl 5.2 gram and Cp
2PtCl
20.01 a gram and a granule iodine crystallization are warming up to 70 ℃ gradually, react 24 hours.After product washes 5 times with water, remove and desolvate, wash for several times with methyl alcohol, drying obtains final product.As can be seen, the peak of oxyethyl group and silicon hydrogen has reduced 85% from infrared and proton magnetic spectrum figure, the peak of hydroxyl is also very weak, illustrates that two ladderlike polymers are by coupling.
Claims (14)
1, a kind of tubular organosilicon polymer.The structural formula that it is characterized in that described tubular organosilicon polymer is as follows:
2, a kind of tubular organosilicon polymer according to claim 1 is characterized in that described structural formula a is two and contains between functional group's ladderlike polymer not of the same race and react to each other and the link coupled tubular high polymer.
3, a kind of tubular organosilicon polymer according to claim 1 is characterized in that described structural formula a is two tubular high polymers that contain functional group's of the same race trapezoidal molecule by coupling agent coupling formation.
4, the preparation method of a kind of tubular organosilicon polymer according to claim 1, it is characterized in that step is carried out in the following order: the organosilicon ladderlike polymer R-T of the reactive active group of band of (1) synthetic high-regularity, R is Vi, Allyl, H, EtO, (2) are by the addition of silicon hydrogen, the oxidation of silicon hydrocarbon or three kinds of linked reaction synthesizing organo-silicons of silicon acyloxylation tubular high polymer.
5, the preparation method of a kind of tubular organosilicon polymer according to claim 4; it is characterized in that described silicon hydrogen addition linked reaction is that Vi-T and H-T or Allyl-T and two kinds of ladderlike polymers of H-T are dissolved in respectively in the exsiccant solvent; mol ratio by 1: 0.8 to 1: 1.5 under the protection of rare gas element adds in the reactor, and adds solvent and Pt
0-1VCompound or Pt
0-1VWith the complex compound of vinyl compound as catalyzer, reactant concn was every milliliter of a 10-40 milligram, 50-120 ℃ of reaction 12-72 hour.
6, the preparation method of a kind of tubular organosilicon polymer according to claim 4; it is characterized in that described silicon hydrogen addition linked reaction is that Vi-T, Allyl-T or H-T are dissolved in the exsiccant solvent; under the protection of rare gas element, add in the reactor, add coupling agent H (SiMe
2O)
mH, CH
2=CH (SiMe
2O)
mCH=CH
2, CH
2=CHCH
2(SiMe
2O)
mCH
2CH=CH
2Or CH
2=CHC
6H
4CH=CH
2, m=1-10 in the formula, n=0-10, and add solvent and Pt
0-1VCompound or Pt
0-1VWith the complex compound of vinyl compound as catalyzer, reactant concn was 540 milligrams every milliliter, 30-100 ℃ of reaction 12-72 hour.
7, the preparation method of a kind of tubular organosilicon polymer according to claim 4; it is characterized in that described silicon hydrocarbon oxidative coupling reaction is that two kinds of ladderlike polymer EtO-T and H-T are dissolved in respectively in the exsiccant solvent; mol ratio by 1: 0.8 to 1: 1.5 under the protection of rare gas element adds in the reactor; and adding solvent and basic catalyst; reactant concn was every milliliter of a 10-40 milligram, 50-120 ℃ of reaction 12-72 hour.
8, the preparation method of a kind of tubular organosilicon polymer according to claim 4; it is characterized in that described silicon hydrocarbon oxidative coupling reaction is that H-T or EtO-T are dissolved in the exsiccant solvent; under the protection of rare gas element, add in the reactor; add the coupling agent Resorcinol to the pure and mild basic cpd of dibenzyl or phenol sodium as catalyzer; reactant concn was 540 milligrams every milliliter, 30-100 ℃ of reaction 12-72 hour.
9, the preparation method of a kind of tubular organosilicon polymer according to claim 4; it is characterized in that described silicon acyloxylation linked reaction is that two kinds of ladderlike polymer EtO-T and H-T are dissolved in respectively in the exsiccant solvent; mol ratio by 1: 0.8 to 1: 1.5 under the protection of rare gas element adds in the reactor; and the complex compound of adding solvent and Pt, iodine is every milliliter of 10-40 milligram as the catalyst reaction substrate concentration.50-120 ℃ of reaction 12-72 hour
10, the preparation method of a kind of tubular organosilicon polymer according to claim 4; it is characterized in that described silicon acyloxylation linked reaction is that ladderlike polymer H-T or EtO-T are dissolved in the exsiccant solvent; under the protection of rare gas element, add in the reactor, add coupling agent HOOC (CH
2)
xCOOH (x=2-10), XOC (C
6H
4) COX, X=halogen, catalyzer are complex compound and the iodine of Pt, reactant concn was every milliliter of a 5-40 milligram, 30-100 ℃ of reaction 12-72 hour.
11, according to claim 6, the preparation method of 8,10 described a kind of tubular organosilicon polymers is characterized in that the coupling of reactant concn for two ladderlike polymers, is every milliliter of 10-40 milligram.
12, according to claim 6, the preparation method of 8,10 described a kind of tubular organosilicon polymers is characterized in that the coupling of reactant concn for ladderlike polymer self side group, is every milliliter of 5-10 milligram.
13, according to claim 6, the preparation method of any tubular organosilicon polymer in 8,10,11,12, the consumption that it is characterized in that the addition of described silicon hydrogen, the oxidation of silicon hydrocarbon, three kinds of linked reaction coupling agents of silicon acyloxylation be the R-T mole number 1.5-0.8 doubly.
14, the purposes of a kind of tubular organosilicon polymer according to claim 1 is characterized in that being used in biosensor, supramolecule catalyzer, supramolecule separatory membrane, novel optical material or novel electricity material.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97112236 CN1206019A (en) | 1997-07-17 | 1997-07-17 | Tubular organosilicon polymer and its preparation and application |
| AU83304/98A AU8330498A (en) | 1997-07-17 | 1998-07-16 | Tube-like organosilicon polymers and the preparation and uses thereof |
| PCT/CN1998/000127 WO1999003911A1 (en) | 1997-07-17 | 1998-07-16 | Tube-like organosilicon polymers and the preparation and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97112236 CN1206019A (en) | 1997-07-17 | 1997-07-17 | Tubular organosilicon polymer and its preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1206019A true CN1206019A (en) | 1999-01-27 |
Family
ID=5172155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97112236 Pending CN1206019A (en) | 1997-07-17 | 1997-07-17 | Tubular organosilicon polymer and its preparation and application |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1206019A (en) |
| AU (1) | AU8330498A (en) |
| WO (1) | WO1999003911A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024691B (en) * | 2006-08-14 | 2010-07-07 | 南京大学 | Self-assembling-growth polysilsesquioxane nano tube and nano wire preparing method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6013740A (en) * | 1998-08-27 | 2000-01-11 | Dow Corning Corporation | Sheet and tube polymers with pendant siloxane groups |
| US6423772B1 (en) | 1999-07-16 | 2002-07-23 | Institute Of Chemistry, Chinese Academy Of Sciences | Organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof, and the method for producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60110726A (en) * | 1983-11-18 | 1985-06-17 | Mitsubishi Electric Corp | Production of silicone compound |
| JPS61278532A (en) * | 1985-06-05 | 1986-12-09 | Mitsubishi Electric Corp | Production of hydroxyphenyl-terminated ladder polysiloxane |
| JP3408549B2 (en) * | 1992-01-23 | 2003-05-19 | 昭和電工株式会社 | Graft-modified ladder silicone and composition thereof |
-
1997
- 1997-07-17 CN CN 97112236 patent/CN1206019A/en active Pending
-
1998
- 1998-07-16 WO PCT/CN1998/000127 patent/WO1999003911A1/en active Application Filing
- 1998-07-16 AU AU83304/98A patent/AU8330498A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024691B (en) * | 2006-08-14 | 2010-07-07 | 南京大学 | Self-assembling-growth polysilsesquioxane nano tube and nano wire preparing method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999003911A1 (en) | 1999-01-28 |
| AU8330498A (en) | 1999-02-10 |
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