CN1796441A - Trapezoidal organic poly sesquisiloxane and preparation method - Google Patents
Trapezoidal organic poly sesquisiloxane and preparation method Download PDFInfo
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- CN1796441A CN1796441A CNA2004101018920A CN200410101892A CN1796441A CN 1796441 A CN1796441 A CN 1796441A CN A2004101018920 A CNA2004101018920 A CN A2004101018920A CN 200410101892 A CN200410101892 A CN 200410101892A CN 1796441 A CN1796441 A CN 1796441A
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Abstract
A preparation method for highly tactic ladder-like polysilsequioxane with solubility, high molecular weight and different organic side groups is introduced in this invention. Trichlorosilicane with different substituents reacts with template-1, 4-dianiline or its derivatives with ladder-brace template method to produce conjugate precursor containing four silicon-chlorine bonds, which self-assembles into ladder polymers by hydrogen bond template function of p-dianiline and transforms into silanol end-capping organic bridging siloxane polymers after hemihydration-hydrolysis-condensation. Such a compound is then end-capped with trimethylsiloxyl and hydrolyzed to remove p-dianiline, and ladder-like polysilsequioxane can be obtained after further condensation. Or tetrafunctional disiloxane monomers with template-function side groups self-assemble into ladder-like polymers, which are then condensation-polymerized and end-capped with trimethylsiloxyl to obtain ladder-like polysilsequioxane.
Description
Technical field
The present invention relates to a kind of trapezoidal organic poly sesquisiloxane.
The invention still further relates to the preparation method of above-mentioned trapezoidal organic poly sesquisiloxane.
Background technology
Nineteen sixty Brown, J.F. etc. (J.Amer.Chem.Soc., 1960,82,6194) reported first is with phenyl triethoxysilane (PhSi (OEt)
3) hydrolyzate is catalyzer with potassium hydroxide at 250 ℃ of warps " balance thermal polycondensation " preparation trapezoidal polyphenyl base silsesquioxane (LPPS).Frye in 1970, C.L. (J.Amer.Chem.Soc., 1971,93,4599) point out that the resulting LPPS of this method is not real ladderlike polymer, but promptly according to the difference of synthesis condition, there is branching in various degree in " short-range order; long-range unordered; contain the many rings cage shape thing that partially opens ".Matsumoto in 2002, H. etc. (J.Amer.Chem.Soc., 1971,93,4599) report adopt chloro-Tuo phenyl reaction to obtain the polysilsesquioxane six aggressiveness crystallizations that side group is different-propyl group.But this method should not prepare superpolymer.Yamamoto in 2004, (Macromolecules, 2004 such as S., 37,2775) reported that phenyl-trichloro-silicane has obtained polyphenylene silsesquioxane oligomer (molecular weight is 1400, and polymerization degree n ≈ 6) with the hydrochloric acid catalysis polycondensation after hydrolysis, infer to have ladder structure, but not with conclusive evidence.(Xie Ping﹠amp such as Zhang Rongben in 1989; Zhang Rongben, Chinese J.Polym.Sci., 1989,2,183) reported first utilizes 1, and 4-Ursol D (PDA) has at first synthesized the hydroxy-end capped trapezoidal poly methyl silsesquioxane of silicon by the method for pre-aminolysis.(Xie Ping such as Zhang Rongben in 1991; Zhang Rongben et al., Chinese J.Polym.Sci., 1991,3,266) reported again with the synthetic hydroxy-end capped polyphenylene silsesquioxane of high-regularity silicon of the pre-amine-decomposing method of PDA.(H-T) and polymkeric substance thereof (Xie Ping such as Zhang Rongben in 1992; ZhangRongben et al., Chinese J.Polym.Sci., 1992,4,361), but this H-T is silicon hydroxyl (Si-OH) end-blocking polymer, its less stable.By trimethylsiloxy group (OSiMe
3) end-blocking, obtained the H-T polymkeric substance of stable performance.Calendar year 2001 Zhang Rongben etc. authorized high regularity polyhydric sesquisiloxane and multipolymer thereof and their method for makings patent (CN 1058730C, JP.4252228).The regularity of the pre-amine-decomposing method synthetic of above-mentioned employing PDA LPRS with
29Represent RSIO among the Si-NMR Spectrum
3/2The half-peak width Δ of resonance absorbing peak
1/2Expression, it is worth Δ
1/2≈ 3-4ppm.Trapezoidal polysilsesquioxane preparation method about other does not see bibliographical information as yet.This shows, so far solubility, high molecular (Mw=10
3～10
6), the trapezoidal polysilsesquioxane (Δ of high-regularity
1/2＜1ppm refers to that branching can ignore) still there is not a maturation method preparation.
Summary of the invention
The purpose of this invention is to provide a kind of trapezoidal organic poly sesquisiloxane.
Another purpose of the present invention is to provide the preparation method of above-mentioned trapezoidal organic poly sesquisiloxane.
For achieving the above object, trapezoidal organic poly sesquisiloxane provided by the invention (LPRS) structure is suc as formula 1:
Formula 1
In the formula: R is saturated or unsaturated alkyl such as alkyl, alkyl, aryl or substituted hydrocarbon radical (comprising: halo, hydroxyl generation, ammonia (amine) base generation, nitroaromatic, epoxy group(ing) for etc.) and derivative thereof.
N is the integer greater than 1, general n=10-500.
Its side group has following structure:
(A) having π-π aryl piles up: the condensed-nuclei aromatics of phenyl, naphthyl, benzo phenanthryl and corresponding derivative;
Containing electronics to give-group of receptor acting, is phenol, ether, alcohol, amine or naphthalene, anthracene, luxuriant and rich with fragrance fragrant condensed ring thing to body wherein; Acceptor is alkene, quinone derivative or the fragrance derivatives of haloalkane, band negative group;
The side group of hydrophobic type effect: the different alkyl chain or derivatives thereofs of length;
(B) have hydrogen bond type side group template, comprising:
Alcoholic extract hydroxyl group, phenolic hydroxyl group, urea groups, amido formate base and aliphatic amide, aromatic amide or derivatives thereof.
The regularity of LPRS shown in the formula 1 is used
29Si-NMR (represents RSIO among the nucleus magnetic resonance) Spectrum
3/2The half-peak width Δ of resonance absorbing peak
1/2Expression, it is worth Δ
1/2＜1ppm.LPRS dissolves in common organic solvents, and molecular weight can be 10
4～10
6Regulate in the scope.
Preparation method provided by the invention, its molecular weight controlled amount, terminal by trimethylsiloxane group (Me
3SiO-) end-blocking is the polymkeric substance of a class stable performance.Proposition simultaneously has the recovery and the purification process of the pre-aminolysis agent (as Ursol D and derivative thereof) of practical value.
LPRS provided by the invention can adopt following preparation method's method.
(1) ladder support template: the trichlorosilane and the template-1 that will have different substituents, the reaction of 4-Ursol D or derivatives thereof, generation contains the conjugate precursor of four silicon chlorine keys, the latter forms trapezoidal aggregate by self-assembly under the hydrogen bond template action of Ursol D, again through " half water-hydrolysis-condensation " (its " half water " refers to use two silicon chlorine of only hydrolysis key institute water requirement), generate solubility, high molecular, high-regularity silicon hydroxyl (≡ Si (OH)-) the trapezoidal poly-organic abutment siloxanes of end-blocking (O-LPRS), use trimethylsiloxy group (≡ Si-OSiMe again
3) behind the end-blocking, the support of Ursol D base ladder is removed in hydrolysis under acidic conditions, further condensation obtains the trapezoidal polysilsesquioxane of solubility, high molecular and high-regularity (LPRS) again.
(2) side group template.The four sense sily oxide monomers that will have template action (comprise pi-pi accumulation between hydrogen bond, aromatic base, electronics give-dissimilar interactions such as acceptor, hydrophobic) side group carry out self-assembly and form trapezoidal aggregate in solution, by polycondensation, adopt the trimethylsiloxy group end-blocking to obtain solubility, high molecular and high-regularity trapezoidal organic poly sesquisiloxane (LPRS) at last again.
It is as follows that terraced hold mode plate legal system of the present invention is equipped with its reaction process of LPRS:
B represents pre-aminolysis agent in the above-mentioned reaction formula, comprises the α of aliphatic series or aromatics, ω-di-primary amine and derivative thereof.Require its alkalescence lower, nontoxic or hypotoxicity, solvable in organic solvent.
Pre-aminolysis agent comprises:
1) aliphatic alpha, ω-di-primary amine and have to its hydrogen bond template do not have destruction draw electron substituent group (as: halogen of location-appropriate, carbonyl, ester group, nitro, cyano group, thiazolinyl, alkynyl, aryl ... etc.) derivative;
R wherein
1, R
2, R
3Be respectively H or the above-mentioned electron substituent group etc. that draws, x=0,1,2,3...＜5 integers.
2) 1,4-Ursol D and having for 1, the hydrogen bond template of 4-Ursol D do not have destruction draw electron substituent group (as: halogen of location-appropriate, carbonyl, ester group, nitro, cyano group and thiazolinyl, alkynyl, aryl ... etc.) derivative;
R wherein
1, R
2, R
3, R
4Be respectively H or the above-mentioned electron substituent group etc. that draws.
3) right-aryl diamine class and have for the hydrogen bond template of aryl diamine is not had destruction draw electron substituent group (as: halogen of location-appropriate, carbonyl, ester group, nitro, cyano group and thiazolinyl, alkynyl, aryl .... etc.) derivative;
Wherein R ' represention oxygen atom, alkylidene group-(CH
2)
n-(wherein n=0,1,2 3......＜5 integers), thiazolinyl, alkynyl or contain groups such as substituent alkylidene group; R
1, R
2, R
3, R
4Be respectively H or the above-mentioned electron substituent group etc. that draws.
The preparation process of trapezoidal organic poly sesquisiloxane (LPRS) is with 1, and the 4-Ursol D is that example is described below as the reaction mechanism of the synthetic trapezoidal polyphenyl base silsesquioxane (LPPS) of pre-aminolysis agent B:
1. α, the pre-aminolysis linked reaction of ω-di-primary amine synthesis of coupling precursor:
2. the coupling monomer is self-assembled into supramolecule hydrogen bond aggregate:
3. the silica-based end-blocking ladder polysiloxane of supramolecule hydrogen bond aggregate condensation prepared end (O-LPRS):
4. prepare ≡ Si-OSiMe
3Base end-blocking organic abutting ladder poly-siloxane:
5. progressively the synthetic ≡ Si-OSiMe of support-condensation reaction is taken off in hydrolysis
3Base end-blocking trapezoidal organic poly sesquisiloxane (LPRS):
Requirement to trapezoidal aggregate condensation reaction catalyst system therefor is to react with side group that Siliciumatom connects, for example: protonic acid, alkali, organic acid, organic bases or metal oxide ... etc.
To the requirement of the used chlorine hydride absorbent of trapezoidal aggregate condensation reaction is the basic cpd, particularly organic amine compound that can not react with side group that Siliciumatom connects.General triethylamine commonly used or pyridine ... etc.
The requirement that support-condensation reaction catalyst system therefor is taken off in hydrolysis progressively be can not with side group that Siliciumatom the connects compound that reacts.For example: protonic acid, alkali, lewis acid, lewis base and organic amine ... etc.
The requirement of pre-aminolysis linked reaction and condensation reaction solvent for use is: (1) should adopt polarity lower; (2) with the molten hydro carbons or derivatives thereof of shipwreck compounds such as (as: alkane, unsaturated olefin, alkynes, aromatic hydrocarbons and halo thereof, carbonyl generation, nitroaromatic, cyano group) generations; (3) do not react with reacting required catalyzer and silicon monomer and reaction intermediate thereof, solvent wherein commonly used is halogenated aryl hydrocarbon or halo naphthenic hydrocarbon (being shown below);
R is: hydrogen, halogen, alkyl, ester cyclic group, nitro, cyano group ... etc.
The requirement of the thinner of double water-hydrolysis-condensation time institute water is: (1) should adopt polarity lower; (2) molten with water; (3) not with the required catalyzer of above-mentioned reaction and not with Siliciumatom the solvent that reacts with side group or silicon hydroxyl.The ketone that for example has following structure, ether compound.
Dioxane, acetone and tetrahydrofuran (THF) commonly used etc. are as diluent water.
Temperature of reaction during double water-hydrolysis-condensation should generally be advisable not to be higher than 50-60 ℃ guaranteeing that hydrogen bond gives full play to the suitable temperature of employing under the template action prerequisite.
The general method for making of the synthetic trapezoidal organic poly sesquisiloxane of ladder support template is as follows:
To fill monomer RSiCl
3Chlorine hydride absorbent (the concentration 2-10g/100ml that adds metering in the reaction flask of solution, triethylamine commonly used) (better temperature is-30-5 ℃ at-50-10 ℃ in the back, optimum temps is-15-10 ℃) fully stir down, the dioxane solution (2-10g/100m1) that then will be dissolved with pre-aminolysis agent lentamente is added drop-wise in the reaction flask, dropwises the back and continues reaction 0.5-2 hour.And then to drip concentration be that water-solvent (being generally ketone or ether solvent) mixed solution of 10-25ml water/100ml carries out half water-hydrolysis-condensation reaction, dropwises the back and continue then to remove by filter the hydrochloride of chlorine hydride absorbent at stirring at room 1-6 hour.Use anhydrous sodium sulfate drying after filtrate decompression removed acetone, get layer Cheongju liquid and carry out end-blocking with the trimethylchlorosilane of calculated amount.The water of adding metering and little amount of catalyst-vitriol oil are hydrolyzed and take off support-condensation reaction then, generally stirred 20-50 hour down at 40 ℃, be preferably 24 hours, wash neutrality with saturated sodium-chloride water solution at last, use anhydrous sodium sulfate drying again, obtain the clear solution of certain density target compound LPRS.Chlorosilane is 2: 1 with the mol ratio of pre-aminolysis agent in the above-mentioned reaction, the mol ratio of end-capping reagent and chlorosilane according to the polymericular weight size 3 * 10
-1～7 * 10
-1Regulate between/1.
The recovery and the purifying of pre-aminolysis agent
Because pre-aminolysis agent is the important source material in this reaction, whether reclaims, and will have influence on the cost of product to a certain extent, the recycling of pre-aminolysis agent is significant for industrial production.The recovery method of pre-aminolysis agent is hydrochloride and the proper amount of sodium hydroxide reactant aqueous solution with pre-aminolysis agent, obtains pre-aminolysis agent crude product, leaves standstill a few hours after-filtration, and recrystallization or distillation then obtains the pure product of pre-aminolysis agent, and general yield is 90～95%.
Side group template of the present invention prepares LPRS and comprises following two kinds.
(A) the aryl pi-pi accumulation, give-acceptor, hydrophobic type or its mating type side group template:
Its general structure is as follows:
Or
N=0,1,2,3...＜10 integers.
(B) hydrogen bond type side group template:
Its general structure is as follows:
For playing the side group of hydrogen bond template action, mainly comprise different alcoholic extract hydroxyl groups, phenolic hydroxyl group, urea groups, amido formate and aliphatic amide and fragrant acid amides and derivative thereof etc.
The reaction mechanism of the synthetic trapezoidal polyphenyl base silsesquioxane (LPPS) of side group template is described below:
A. be self-assembled into trapezoidal supramolecular aggregation;
B. trapezoidal supramolecular aggregation hydrolysis-condensation or half water-hydrolysis-condensation prepare the hydroxy-end capped trapezoidal polysilsesquioxane of silicon;
C. the synthetic trapezoidal polysilsesquioxane LPRS of trimethylsiloxy group end-blocking.
The requirement of offside base template catalyst system therefor is divided into following situation according to side group template dissimilar: if Siliciumatom has and draws electron substituent group should use basic catalyst, as organic aminated compounds, triethylamine Tributylamine, tetrabutylammonium hydroxide phosphine and tetramethyl-oxyammonia commonly used ... etc.If Siliciumatom has and pushes away electron substituent group and should use an acidic catalyst,, use hydrochloric acid or sulfuric acid always and be advisable as mineral acid or organic acid compound.
The requirement of offside base template solvent for use is divided into following situation according to side group template dissimilar: (1) should adopt polarity lower for its hydrogen bond type side group template; Molten with shipwreck; And the hydro carbons or derivatives thereof that does not react with preparation required catalyzer and silicon monomer and reaction intermediate thereof compounds such as (as: alkane, unsaturated olefin, alkynes, aromatic hydrocarbons and halo thereof, carbonyl generation, nitroaromatic, cyano group) generations.(2) for aryl accumulation type or electronics give-acceptor side group template need select to have suitable polar solvent so that strengthen its template action and guarantee to carry out polymerization under homogeneous system.
Requirement to the thinner of hydrolysis-condensation or half water-hydrolysis-condensation reaction institute water is: (1) should adopt polarity lower; (2) can be easily molten with water; (3) not with reaction required catalyzer or Siliciumatom the solvent that reacts with side group or silicon hydroxyl.For example: ether (as dioxane, tetrahydrofuran (THF) etc.) or ketone compounds.
The temperature of reaction that is adopted during double water-hydrolysis-condensation should generally be advisable in room temperature-200 a ℃ scope guaranteeing that side group gives full play to the suitable temperature of employing under the template action prerequisite.
The general method for making of the synthetic trapezoidal organic poly sesquisiloxane of side group template is as follows:
(A) aryl accumulation type side group template
Reflux condensing tube is being housed; magnetic stirring apparatus also is connected with in vacuum row's the 50mL Schlenk bottle; the coupling agent that adds the rapping plate effect; under argon shield; add solvent (toluene or tetrahydrofuran (THF) by every 2mmol coupling agent; concentration 0.05～0.2g/mL)) and the sily oxide coupling agent 1mmol of equivalent; reacted 48～120 hours down at 70～100 ℃; except that after desolvating; be hydrolyzed about 10-20 hour down at 0～30 ℃ with being dissolved with tetrahydrofuran (THF)/aqueous solution that 2-3 drips the dilute hydrochloric acid of 1M; tetrahydrofuran (THF)/aqueous solution is 10/1 by volume, washes with water to neutrality again.After siccative (anhydrous sodium sulphate generally commonly used) drying, remove by filter that solid to be added 20-50ml concentration behind the solvent behind recrystallization purifying be 1 of 0.3-1g/mL, 1,2, the 2-tetrachloroethane and with the reactant quality than the azeotropic water removing condensation of reducing pressure of catalyzer-Tetramethylammonium hydroxide of 0.5-1%, 60～120 ℃ of temperature of reaction, 24～48 hours reaction times.Under except that the follow-up continuous decompression of desolvating, fully dewater, carry out solid state polymerization.Product is dissolved in the sherwood oil, through volume ratio be 1: 1 methanol/ethanol precipitate a light brown solid LPRS.
(B) hydrogen bond type side group template
The coupling silicon monomer that will have-two hydrogen bond template side group tetraalkoxysilanes add in the chlorobenzene, and monomer concentration is the solution of 2～8g/100mL.Splash into 2-3 under the room temperature and drip the dioxane aqueous solution that begins to drip calculated amount behind the vitriol oil. reacted again after the dropping 30-50 hour.The triethylamine neutralisation of sulphuric acid of adding and vitriol oil equivalent is filtered, and removes triethylamine vitriol.Drip 3-4 then and drip organotin (generally using dibutyl tin dilaurate) catalyzer, continue reaction at 20-50 ℃ and carried out dealcoholization condensation reaction in 48-60 hour, the reaction back adds petroleum ether precipitation and goes out white polymer in condensated liquid.The gained white solid is dissolved in the tetrahydrofuran (THF), and adding excessive trimethylchlorosilane a few hours of refluxing carries out end capping, adds petroleum ether precipitation at last and goes out white polymer LPRS.
Trapezoidal organic poly sesquisiloxane of the present invention has excellent thermotolerance, radioresistance, film-forming properties and dielectric properties and good mechanical performance and workability because main chain is trapezoidal duplex structure and the organic side group that inorganic Si-O-Si-key constitutes.Having widespread use in light-electricity, chemical industry, biology-medical or building material field is worth
Effect of the present invention:
The polymkeric substance salient features sees Table 1:
The performance of the trapezoidal polysilsesquioxane LPRS of table 1 high-regularity
| Phenyl | 5×10 3 | Dissolving | 91 | 14.3 | 4.6 | ＜1 |
| Phenyl | 7×10 5 | Dissolving | 95 | 14.4 | 4.6 | ＜1 |
| Benzophenanthrene | 8×10 5 | Dissolving | 98 | 32.3 | 13.8 | ＜0.5 |
| Benzamide | 6×10 5 | Dissolving | 94 | 16.5 | 4.2 | ＜1.5 |
| Fatty amide | 4×10 5 | Dissolving | 90 | 36.8 | 4.3 | ＜1.5 |
This polymkeric substance (LPRS) is solubility, high regular ladderlike polymer, and its regularity is used
29Represent RSIO among the Si-NMR Spectrum (being illustrated in fig. 1 shown below)
3/2The half-peak width Δ of resonance absorbing peak
1/2Expression, it is worth Δ
1/2＜1ppm, molecular weight can be 10
3～10
6Regulate in the interior scope.
Description of drawings
Fig. 1 is the trapezoidal polysilsesquioxane LPRS of a present invention solid
29Si-NMR composes (Δ
1/2Value＜0.5ppm).
Embodiment
Embodiment 1
The 50ml dioxane solution that will contain 1.08g (10mmol) PDA under stirring is added drop-wise to and contains 4.3g (20mmol) phenyl-trichloro-silicane (PhSiCl
3) and the 50ml chlorobenzene solution of 6.1g (60mmol) triethylamine (TEA) in, temperature maintenance is at 0 ℃, drip the 10ml dioxane solution that contains 0.36ml (20mmol) water after stirring half an hour, 3 hours after-filtration of stirring at room, its filtrate is removed most of solvent with rotatory evaporator, add anhydrous sodium sulfate drying, take out the upper strata drying solution add closure agent trimethylchlorosilane 10.8mg (0.10mmol) end-blocking then add 0.13g water and and 1-5 drip the vitriol oil and under 40 degree, stirred 24 hours, be washed till neutrality with saturated sodium-chloride water solution again, use anhydrous sodium sulfate drying, obtain trapezoidal polyphenyl base silsesquioxane water white transparency toluene solution, concentration is 15mg/ml productive rate 85%, and molecular weight that light scattering method is surveyed is 1.0
5* 10
5, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 2
The 25ml dioxane solution that will contain 1.08g (10mmol) PDA under stirring is added drop-wise to and contains 3.0g (20mmol) METHYL TRICHLORO SILANE (MeSiCl
3) and the 40ml toluene solution of 6.1g (60mmol) triethylamine (TEA) in, temperature is controlled at about-15 ℃, stir half an hour, the 20ml dioxane solution that will contain 0.36ml (20mmol) water again splashes into reaction flask, at room temperature stir filtration in 4 hours, its filtrate is removed most of solvent with rotatory evaporator, use anhydrous sodium sulfate drying, filtration obtains adding under the filtrate stirring 10.8mg (0.10mmol) closure agent trimethylchlorosilane and carries out end-blocking, then add 0.23g water and 1-5 and drip the vitriol oil, stirred three hours under the room temperature, be warming up to 80-90 ℃ and stirred 5 hours, the back is washed till neutrality with saturated sodium-chloride water solution, obtains colourless transparent solution with anhydrous sodium sulfate drying, its concentration is 15-20mg/ml, productive rate 90%.Get the trapezoidal poly methyl silsesquioxane of product, it is 5 * 10 that light scattering method is surveyed molecular weight
4Its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 3
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 2.16g (20mmol) under stirring is added drop-wise to and contains 6.5g (40mmol) vinyl trichloro silane (CH
2=CHSiCl
3) and the 80ml chlorobenzene solution of 12.2g (120mmol) triethylamine (TEA) in, temperature maintenance is about-20 ℃, continuing to stir the 10ml tetrahydrofuran solution that will contain 0.72g (40mmol) water half an hour then after dropwising slowly is added drop-wise in the reaction flask, stirred 4 hours, filter, filtrate is removed 1/2nd solvents with Rotary Evaporators, remaining chlorobenzene solution anhydrous Na
2SO
4Drying is got supernatant liquid 21.8mg (0.20mmol) trimethylchlorosilane (Me
3SiCl) end socket, adding 0.6g water and 1-5 drips the vitriol oil and takes off support reduction and close, at room temperature stir after 24 hours and be washed till neutrality with saturated sodium-chloride water solution, spend the night with anhydrous sodium sulfate drying again, the clear, colorless toluene solution that obtains, its concentration is 10mg/ml, and high vacuum dry can get product 2.5g, productive rate 70-76%.It is 6.4 * 10 that light scattering method is surveyed molecular weight
4Its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 4
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 1.08g (10mmol) under stirring is added drop-wise to and contains 3.6g (20mmol) allyltrichlorosilane (CH
2CHCH
2SiCl
3) and the 100ml toluene solution of 6.06g (60mmol) triethylamine (TEA) in, temperature maintenance is at-20～-15 ℃, drip the back and stir half an hour, drip the 15ml dioxane solution that contains 0.36ml (20mmol) water down at-10 ℃ again, stirred 3 hours under the room temperature, after the filtration filtrate is removed most of solvent with rotatory evaporator, add 10.8mg (0.10mmol) closure agent Me
3The SiCl end-blocking then adds 0.7g water and 5-15 and drips the vitriol oil, stirs 24 hours down at 40 ℃, the back is washed till neutrality with saturated sodium-chloride water solution, adds anhydrous sodium sulfate drying, obtains the water white transparency toluene solution, concentration is 10mg/ml, and product yield is 90%, and it is 7.3 * 10 that light scattering method is surveyed molecular weight
4Its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 5:
The 50ml tetrahydrofuran solution that will contain 2.16g (20mmol) PDA under stirring is added drop-wise to and contains 8.7g (40mmol) cyclohexyl trichlorosilane (C
6H
11SiCl
3) and the 100ml toluene solution of 12.2g (120mmol) triethylamine in, temperature is controlled at about-15 ℃, stir half an hour, the 20ml tetrahydrofuran solution that will contain 0.72g (40mmol) water again splashes into, at room temperature stirred 4 hours, use anhydrous sodium sulfate drying, filtration obtains filtrate and stirs adding 21.6mg (0.20mmol) closure agent trimethylchlorosilane end-blocking down, then add 0.7g water and 1-5 and drip the vitriol oil, stirred three hours under the room temperature, be warming up to 80-90 ℃ and stirred 5 hours, the back is washed till neutrality with saturated sodium-chloride water solution, obtain colourless transparent solution with anhydrous sodium sulfate drying, its concentration is 15-20mg/ml, productive rate 90%.Get the trapezoidal poly methyl silsesquioxane of product, it is 1.12 * 10 that light scattering method is surveyed molecular weight
5Its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 6
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 1.08g (10mmol) under stirring is added drop-wise to and contains 3.7g (20mmol) chloromethyl trichlorosilane (ClCH
2SiCl
3) and the 100ml toluene solution of 6.1g (60mmol) triethylamine (TEA) in, stir, temperature maintenance is at-20～-15 ℃, drip the back and stir half an hour, drip the solution that contains 0.36ml (20mmol) water dioxane down at-10 ℃ again, stirred 3 hours under the room temperature, add 10.8mg (0.10mmol) closure agent Me in the filtration rear filtrate
3The SiCl end-blocking, then add 0.7g water and 5-15 and drip the vitriol oil, stirred 24 hours down at 40 ℃, the back is washed till neutrality with saturated sodium-chloride water solution, add anhydrous sodium sulfate drying, obtain the water white transparency toluene solution, concentration is 10mg/ml, product yield is 90%, and molecular weight that light scattering method is surveyed is 0.91 * 10
5, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 7
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 1.08g (10mmol) under stirring is added drop-wise to and contains 4.2g (20mmol) chloropropyl trichloro-silane (ClCH
2CH
2CH
2SiCl
3) and the 100ml toluene solution of 6.1g (60mmol) triethylamine (TEA) in, stir, temperature maintenance is at-20～-15 ℃, drip the back and stir half an hour, drip the solution that contains 0.36ml (20mmol) water dioxane down at-10 ℃ again, stirred 3 hours under the room temperature, add 108mg (1mmol) closure agent Me in the filtration rear filtrate
3The SiCl end-blocking, then add 0.7g water and 5-15 and drip the vitriol oil, stirred 24 hours down at 40 ℃, the back is washed till neutrality with saturated sodium-chloride water solution, add anhydrous sodium sulfate drying, obtain the water white transparency toluene solution, concentration is 10mg/ml, product yield is 91%, and molecular weight that light scattering method is surveyed is 9.1 * 10
3, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 8
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 2.16g (20mmol) under stirring is added drop-wise to and contains 7.2g (40mmol) sec.-propyl trichlorosilane (CH
3CH
3CHSiCl
3) and the 80ml chlorobenzene solution of 12.2g (120mmol) triethylamine (TEA) in, temperature maintenance is about-20 ℃, continuing to stir the 10ml tetrahydrofuran solution that will contain 0.72g (40mmol) water half an hour then after dropwising slowly is added drop-wise in the reaction flask, stirred 4 hours, filter, filtrate is removed 1/2nd solvents with Rotary Evaporators, remaining chlorobenzene solution anhydrous Na
2SO
4Drying is got supernatant liquid 2.17mg (0.020mmol) trimethylchlorosilane (Me
3SiCl) end socket, adding 0.6g water and 1-5 drips the vitriol oil and takes off support reduction and close, at room temperature stir after 24 hours and be washed till neutrality with saturated sodium-chloride water solution, spend the night with anhydrous sodium sulfate drying again, the clear, colorless toluene solution that obtains, its concentration is 10mg/ml, and high vacuum dry can get product 2.5g, productive rate 70-76%.It is 9.4 * 10 that light scattering method is surveyed molecular weight
5Its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 9
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 1.08g (10mmol) under stirring is added drop-wise to and contains 5.3g (20mmol) naphthyl trichlorosilane (C
10H
7SiCl
3) and the 100ml toluene solution of 6.1g (60mmol) triethylamine (TEA) in, stir, temperature maintenance is at-20～-15 ℃, drip the back and stir half an hour, drip the solution that contains 0.36ml (20mmol) water dioxane down at-10 ℃ again, stirred 3 hours under the room temperature, add 10.8mg (0.10mmol) closure agent Me in the filtration rear filtrate
3The SiCl end-blocking, then add 0.7g water and 5-15 and drip the vitriol oil, stirred 24 hours down at 40 ℃, the back is washed till neutrality with saturated sodium-chloride water solution, add anhydrous sodium sulfate drying, obtain the water white transparency toluene solution, concentration is 10mg/ml, product yield is 90%, and molecular weight that light scattering method is surveyed is 1.3 * 10
5, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 10
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 1.08g (10mmol) under stirring is added drop-wise to and contains 5.0g (20mmol) octyl group trichlorosilane (C
8H
17SiCl
3) and the 100ml toluene solution of 6.1g (60mmol) triethylamine (TEA) in, stir, temperature maintenance is at-20～-15 ℃, drip the back and stir half an hour, drip the solution that contains 0.36ml (20mmol) water dioxane down at-10 ℃ again, stirred 3 hours under the room temperature, add 10.8mg (0.10mmol) closure agent Me in the filtration rear filtrate
3The SiCl end-blocking, then add 0.7g water and 5-15 and drip the vitriol oil, stirred 24 hours down at 40 ℃, the back is washed till neutrality with saturated sodium-chloride water solution, add anhydrous sodium sulfate drying, obtain the water white transparency toluene solution, concentration is 10mg/ml, product yield is 90%, and molecular weight that light scattering method is surveyed is 1.15 * 10
5, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 11
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 1.08g (10mmol) under stirring is added drop-wise to and contains 6.07g (20mmol) dodecyl trichlorosilane (CH
3(CH
2)
10CH
2SiCl
3) and the 100ml toluene solution of 6.1g (60mmol) triethylamine (TEA) in, stir, temperature maintenance is at-20～-15 ℃, drip the back and stir half an hour, drip the solution that contains 0.36ml (20mmol) water dioxane down at-10 ℃ again, stirred 3 hours under the room temperature, add 108mg (1mmol) closure agent Me in the filtration rear filtrate
3The SiCl end-blocking, then add 0.7g water and 5-15 and drip the vitriol oil, stirred 24 hours down at 40 ℃, the back is washed till neutrality with saturated sodium-chloride water solution, add anhydrous sodium sulfate drying, obtain the water white transparency toluene solution, concentration is 10mg/ml, product yield is 91%, and molecular weight that light scattering method is surveyed is 9.1 * 10
3, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 12
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 2.16g (20mmol) under stirring is added drop-wise to and contains 10.6g (40mmol) p-chlorophenyl trichlorosilane (p-ClC
6H
4SiCl
3) and the 80ml chlorobenzene solution of 12.2g (120mmol) triethylamine (TEA) in, temperature maintenance is about-20 ℃, continuing to stir the 10ml tetrahydrofuran solution that will contain 0.72g (40mmol) water half an hour then after dropwising slowly is added drop-wise in the reaction flask, stirred 4 hours, filter, filtrate is removed 1/2nd solvents with Rotary Evaporators, remaining chlorobenzene solution anhydrous Na
2SO
4Drying is got supernatant liquid 2.17mg (0.020mmol) trimethylchlorosilane (Me
3SiCl) end socket, adding 0.6g water and 1-5 drips the vitriol oil and takes off support reduction and close, at room temperature stir after 24 hours and be washed till neutrality with saturated sodium-chloride water solution, spend the night with anhydrous sodium sulfate drying again, the clear, colorless toluene solution that obtains, its concentration is 10mg/ml, and high vacuum dry can get product 2.5g, productive rate 70-76%.It is 9.4 * 10 that light scattering method is surveyed molecular weight
5Its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 13
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 1.08g (10mmo1) under stirring is added drop-wise to and contains 5.76g (20mmo1) to ethylphenyl trichlorosilane (p-EtC
6H
4SiCl
3) and the 100ml toluene solution of 6.1g (60mmol) triethylamine (TEA) in, stir, temperature maintenance is at-20～-15 ℃, drip the back and stir half an hour, drip the solution that contains 0.36ml (20mmol) water dioxane down at-10 ℃ again, stirred 3 hours under the room temperature, add 108mg (1mmol) closure agent Me in the filtration rear filtrate
3The SiCl end-blocking, then add 0.7g water and 5-15 and drip the vitriol oil, stirred 24 hours down at 40 ℃, the back is washed till neutrality with saturated sodium-chloride water solution, add anhydrous sodium sulfate drying, obtain the water white transparency toluene solution, concentration is 10mg/ml, product yield is 91%, and molecular weight that light scattering method is surveyed is 9.1 * 10
3, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 14
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 1.08g (10mmol) under stirring is added drop-wise to and contains 5.8g (20mmol) p-methoxyphenyl base trichlorosilane (p-CH
3OC
6H
4SiCl
3) and the 100ml toluene solution of 6.1g (60mmol) triethylamine (TEA) in, stir, temperature maintenance is at-20～-15 ℃, drip the back and stir half an hour, drip the solution that contains 0.36ml (20mmol) water dioxane down at-10 ℃ again, stirred 3 hours under the room temperature, add 108mg (1mmol) closure agent Me in the filtration rear filtrate
3The SiCl end-blocking, then add 0.7g water and 5-15 and drip the vitriol oil, stirred 24 hours down at 40 ℃, the back is washed till neutrality with saturated sodium-chloride water solution, add anhydrous sodium sulfate drying, obtain the water white transparency toluene solution, concentration is 10mg/ml, product yield is 91%, and molecular weight that light scattering method is surveyed is 9.1 * 10
3, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 15
The dioxane solution 50ml that will contain the pre-aminolysis agent PDA of 1.08g (10mmol) under stirring is added drop-wise to and contains 3.2g (20mmol) ethynyl trichlorosilane (CH ≡ CSiCl
3) and the 100ml toluene solution of 6.1g (60mmol) triethylamine (TEA) in, stir, temperature maintenance is at-20～-15 ℃, drip the back and stir half an hour, drip the solution that contains 0.36ml (20mmol) water dioxane down at-10 ℃ again, stirred 3 hours under the room temperature, add 10.8mg (0.10mmol) closure agent Me in the filtration rear filtrate
3The SiCl end-blocking, then add 0.7g water and 5-15 and drip the vitriol oil, stirred 24 hours down at 40 ℃, the back is washed till neutrality with saturated sodium-chloride water solution, add anhydrous sodium sulfate drying, obtain the water white transparency toluene solution, concentration is 10mg/ml, product yield is 90%, and molecular weight that light scattering method is surveyed is 4.2 * 10
4, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 16
Reflux condensing tube is being housed, and magnetic stirring apparatus also is connected with in vacuum row's the 100mLSchlenk bottle, adds micro-Cp
2PtCl
2Catalyzer and 1.25g (1.9mmol) 2-allyl group-3-methoxyl group-6; 7; 10; 11-pentyloxy benzo phenanthrene; under argon shield; add 20mL tetrahydrofuran (THF) and 0.1880g (9.5mmol) tetramethoxy sily oxide; refluxing down, reaction was chilled to room temperature in 96 hours. add the tetrahydrofuran (THF) of 1～2 dilute hydrochloric acid and the mixed solvent hydrolysis of water; wash with water again to neutrality; dry. remove the back of desolvating and add 10mL1; 1,2, remove after 2-tetrachloroethane and a small amount of Tetramethylammonium hydroxide reduced pressure azeotropic water removing .48 hour and desolvate; under 120 ℃, carry out solid state polymerization; decompression fully dewaters down, and final product is dissolved in the sherwood oil, the methanol/ethanol through 1: 1 precipitate the khaki color solid.Yield 85%. is dissolvable in water in the common organic solvents such as sherwood oil, acetone and tetrahydrofuran (THF).X-ray diffraction (XRD) shows the width d of ladder
1=35.6 thickness d
2=18.9 ; Molecular weight that light scattering method is surveyed is 8.0 * 10
5, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 17
Reflux condensing tube is being housed, and magnetic stirring apparatus also is connected with in vacuum row's the 100mLSchlenk bottle, adds micro-Cp
2PtCl
2Catalyzer and 1.14g (1.9mmol) 2-allyl group-3-methoxyl group-6; 7; 10; 11-butoxy benzo phenanthrene; under argon shield; add 20mL tetrahydrofuran (THF) and 0.1880g (9.5mmol) tetramethoxy sily oxide; refluxing down, reaction was chilled to room temperature in 96 hours. add the tetrahydrofuran (THF) of 1～2 dilute hydrochloric acid and the mixed solvent hydrolysis of water; wash with water again to neutrality; dry. remove the back of desolvating and add 10mL1; 1,2, remove after 2-tetrachloroethane and a small amount of Tetramethylammonium hydroxide reduced pressure azeotropic water removing .48 hour and desolvate; under 120 ℃, carry out solid state polymerization; decompression fully dewaters down, and final product is dissolved in the sherwood oil, the methanol/ethanol through 1: 1 precipitate the khaki color solid.Yield 85%. is dissolvable in water in the common organic solvents such as sherwood oil, acetone and tetrahydrofuran (THF).X-ray diffraction (XRD) shows the width d of ladder
1=32.3 thickness d
2=16.8 ; Molecular weight that light scattering method is surveyed is 8.2 * 10
5, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 18
Reflux condensing tube is being housed, and magnetic stirring apparatus also is connected with in vacuum row's the 100mLSchlenk bottle, adds micro-Cp
2PtCl
2Catalyzer and 1.04g (1.9mmol) 2-allyl group-3-methoxyl group-6; 7; 10; 11-propoxy-benzophenanthrene; under argon shield; add 20mL tetrahydrofuran (THF) and 0.1880g (9.5mmol) tetramethoxy sily oxide; refluxing down, reaction was chilled to room temperature in 96 hours. add the tetrahydrofuran (THF) of 1～2 dilute hydrochloric acid and the mixed solvent hydrolysis of water; wash with water again to neutrality; dry. remove the back of desolvating and add 10mL1; 1,2, remove after 2-tetrachloroethane and a small amount of Tetramethylammonium hydroxide reduced pressure azeotropic water removing .48 hour and desolvate; under 120 ℃, carry out solid state polymerization; decompression fully dewaters down, and final product is dissolved in the sherwood oil, the methanol/ethanol through 1: 1 precipitate the khaki color solid.Yield 88%. is dissolvable in water in the common organic solvents such as sherwood oil, acetone and tetrahydrofuran (THF).X-ray diffraction (XRD) shows the width d of ladder
1=30.1 thickness d
2=13.8 ; Molecular weight that light scattering method is surveyed is 8.9 * 10
5, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 19
Reflux condensing tube is being housed, and magnetic stirring apparatus also is connected with in vacuum row's the 100mLSchlenk bottle, adds micro-Cp
2PtCl
2Catalyzer and 0.93g (1.9mmol) 2-allyl group-3-methoxyl group-6; 7; 10; 11-pentyloxy benzo phenanthrene; under argon shield; add 20mL tetrahydrofuran (THF) and 0.1880g (9.5mmol) tetramethoxy sily oxide; refluxing down, reaction was chilled to room temperature in 96 hours. add the tetrahydrofuran (THF) of 1～2 dilute hydrochloric acid and the mixed solvent hydrolysis of water; wash with water again to neutrality; dry. remove the back of desolvating and add 10mL1; 1,2, remove after 2-tetrachloroethane and a small amount of Tetramethylammonium hydroxide reduced pressure azeotropic water removing .48 hour and desolvate; under 120 ℃, carry out solid state polymerization; decompression fully dewaters down, and final product is dissolved in the sherwood oil, the methanol/ethanol through 1: 1 precipitate pale brown look solid.Yield 90%. is dissolvable in water in the common organic solvents such as sherwood oil, acetone and tetrahydrofuran (THF).X-ray diffraction (XRD) shows the width d of ladder
1=29.6 thickness d
2=12.5 ; Molecular weight that light scattering method is surveyed is 9.2 * 10
5, its toluene solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜1ppm shows that its regularity is good.
Embodiment 20
Reflux condensing tube is being housed, and magnetic stirring apparatus also is connected with in vacuum row's the 50mLSchlenk bottle, adds micro-Cp
2PtCl
2Catalyzer and 0.4040g (1.0mmol) 2-allyl group-5-pentyloxy-1; the dihydropyrane ether of 4-Resorcinol; under argon shield; add 20mL tetrahydrofuran (THF) and 0.0990g (5.0mmol) tetramethoxy sily oxide; 40 ℃ are reacted down after 36 hours except that desolvating; add 20mL anhydrous methanol and two acidifying petroleum ether and stirring after 1 hour, use 1NNaCO
3After solution is washed till pH=5～6. remove most of ethanol, carries out post and separate, monomer M
1
With 0.4974g (7.4mmol) monomer M
1Be dissolved among the 100mL NMP, drip 1.5g anhydrous sodium sulphate and 1.3g silver suboxide, stirring at room is 3 hours under the argon shield, filters out sodium sulfate, and NMP is removed in decompression, carries out the post separation and obtains monomer M
2
In the 250mL flask, add 0.3685g (5.5mmol) monomer M
1And 0.3330g (5.0mmol) monomer M
2, 0 ℃ drips down 10mL methyl alcohol and 30mL acetone and 1.0mL 1N dilute hydrochloric acid, 40 ℃ of following vigorous stirring 15 hours.Remove most of acetone, carried out azeotropic water removing 6 days, drip 15mL water, the sedimentation and filtration that produces is collected vacuum-drying. the gained solid adds 30mL dimethylbenzene, the aqueous solution of 60mL anhydrous methanol and several 0.1M Tetramethylammonium hydroxide, under reflux temperature, stirred 4 hours, remove the second alcohol and water and rise to 130 ℃ until temperature, reflux under this temperature and removed Tetramethylammonium hydroxide in 5 hours, concentrated solution obtains brown solid. and yield 75%. dissolves in THF, NMP and the DMF isopolarity solvent; XRD shows the width d of ladder
1=28.5 , thickness d
2=11.2 are.Molecular weight that light scattering method is surveyed is 1.2 * 10
5, its solution is used
29Si-NMR measures the peak width at half height Δ
1/2＜0.5ppm shows that its regularity is good.
Embodiment 21
The monomer that 2.88 grams (5mmol) is had side group aramid hydrogen bond adds in 80 milliliters of chlorobenzenes, treat to splash into two vitriol oils after the monomer dissolving, and then drip 0.18 the gram (10mmol) water dioxane solution, drip the back in room temperature reaction 24 hours, in reaction mixture, add the salt that neutralizes with the isodose triethylamine of the vitriol oil and leach generation.In reaction mixture, drip 4 organotin catalysts continuation reactions then and carried out dealcoholization in 48 hours. reaction is mixed clear liquid add the polymkeric substance that settles out in 150 milliliters of sherwood oils, the gained white solid is dissolved in the tetrahydrofuran (THF), in solution, add several trimethylchlorosilanes backflows and carried out end-blocking in three hours, final reaction mixing clear liquid adds the white polymer of wanting that settles out in 200 milliliters of sherwood oils. get polymkeric substance 1.82 grams. and yield is 79%, this polymkeric substance dissolves in tetrahydrofuran (THF), acetone equal solvent, light scattering method record molecular weight 6 * 10
5, its tetrahydrofuran solution is used for
29The mensuration of Si-NMR, its peak width at half height Δ
1/2＜1.5ppm shows that its regularity is fine.
Embodiment 22
The monomer that 5.00 grams (6mmol) is had pendant aliphatic acid amides hydrogen bond adds in 100 milliliters of chlorobenzenes, splash into two vitriol oils after the monomer dissolving, stir the dioxane solution that drips 0.22 (12mmol) gram water down, drip the back in room temperature reaction 30 hours. in reaction mixture, add the salt that neutralizes with the isodose triethylamine of the vitriol oil and leach generation. in reaction mixture, add 3 organotin catalysts then and continue reaction and carried out dealcoholization in 48 hours. reaction is mixed the polymkeric substance that settles out in 150 milliliters of sherwood oils of clear liquid adding,. again the gained white solid is dissolved in the tetrahydrofuran (THF), in solution, add 0.5 milliliter of trimethylchlorosilane backflow and carried out end-blocking in four hours, final reaction mixing clear liquid adds the white polymer of wanting that settles out in 200 milliliters of sherwood oils. get white solid 4.02 grams, yield is 93%, this polymkeric substance dissolves in tetrahydrofuran (THF), acetone equal solvent, light scattering method record molecular weight 8.5 * 10
5, its tetrahydrofuran solution is used for
29The mensuration of Si-NMR, peak width at half height value Δ
1/2＜1.5ppm shows that its regularity is better.
Embodiment 23
Under ice-water bath, with 1.5 milliliters of 1N hydrochloric acid, 60 milliliters of acetone, the mixed solution of 40 milliliters of anhydrous methanols and 20 milliliters of diethylene glycol dimethyl ethers slowly is added to and contains 3.46 gram (0.01 moles) 2, the two tetrahydropyranyl ethers of 5-two [3-(methyl dimethoxy oxygen base is silica-based) n-propyl] Resorcinol, in the reaction flask of 80 milliliters of toluene and 50 milliliters of acetone, rise to room temperature after adding and continue reaction 24 hours.It is low to screw out most of acetone and methyl alcohol, adds two vitriol oils as condensation catalyst, and temperature of reaction is controlled at 50 ℃.The water that produces in the condensation course is removed by indirect decompression, in this process 40 milliliters of toluene is added in batches.Condensation four days adds the polymkeric substance that settles out in the bulk petroleum ether to reaction mixture.Again resulting polymers being dissolved in the tetrahydrofuran (THF), adding several trimethylchlorosilanes backflows and carried out end-blocking in five hours, in reaction solution adding sherwood oil, be settled out white polymer at last. yield is 90%.This polymkeric substance dissolves in tetrahydrofuran (THF), and acetone equal solvent, light scattering method record molecular weight 5.3 * 10
5Its
29Si-NMR measures its peak width at half height value Δ
1/2＜1.5ppm shows that its regularity is better.
Embodiment 24
The monomer that 3.66 grams (5mmol) is had side group laurylamide hydrogen bond adds in 100 milliliters of dioxane, treat to splash into three vitriol oils after the monomer dissolving, and then drip 0.18 the gram (10mmol) water dioxane solution, drip the back in room temperature reaction 30 hours, in reaction mixture, add the salt that neutralizes with the isodose triethylamine of the vitriol oil and leach generation.In reaction mixture, add 4 organotin catalysts continuation reactions then and carried out dealcoholization in 50 hours. reaction is mixed clear liquid add the polymkeric substance that settles out in 200 milliliters of sherwood oils, molten again in tetrahydrofuran (THF) the gained white solid, in solution, add 0.5 milliliter of trimethylchlorosilane backflow and carried out end-blocking in 5 hours, final reaction mixing clear liquid adds the white polymer of wanting that settles out in 200 milliliters of sherwood oils. get polymkeric substance 2.51 grams. and yield is 86%, this polymkeric substance dissolves in tetrahydrofuran (THF), acetone equal solvent, light scattering method record molecular weight 7.1 * 10
5, its tetrahydrofuran solution is used for
29The mensuration of Si-NMR, its peak width at half height Δ
1/2＜1ppm shows that its regularity is fine.
Embodiment 25
The monomer that 4.5 grams (5mmol) are had a side group stearic amide hydrogen bond adds in 80 milliliters of chlorobenzenes and the 40 milliliters of dioxane mixing solutionss, treat to splash into two vitriol oils after the monomer dissolving, and then drip 0.18 the gram (10mmol) water dioxane solution, drip the back in room temperature reaction 20 hours, in reaction mixture, add the salt that neutralizes with the isodose triethylamine of the vitriol oil and leach generation.In reaction mixture, add 4 organotin catalysts continuation reactions then and carried out dealcoholization in 50 hours. reaction is mixed clear liquid add the polymkeric substance that settles out in 150 milliliters of sherwood oils, the gained white solid is dissolved in the tetrahydrofuran (THF), in solution, add 0.5 milliliter of trimethylchlorosilane backflow and carried out end-blocking in 4 hours, final reaction mixing clear liquid adds the white polymer of wanting that settles out in 200 milliliters of sherwood oils. get polymkeric substance 3.00 grams. and yield is 80%, this polymkeric substance dissolves in tetrahydrofuran (THF), acetone, toluene equal solvent, light scattering method record molecular weight 8.5 * 10
5, its tetrahydrofuran solution is used for
29The mensuration of Si-NMR, its peak width at half height Δ
1/2＜1ppm shows that its regularity is fine
Embodiment 26
The monomer that 3.48 grams (5mmol) is had side group naphthalene amino acid hydrogen bond adds in 90 milliliters of chlorobenzenes, treat to splash into two vitriol oils after the monomer dissolving, and then drip 0.18 the gram (10mmol) water dioxane solution, drip the back in room temperature reaction 36 hours, in reaction mixture, add the salt that neutralizes with the isodose triethylamine of the vitriol oil and leach generation.In reaction mixture, add 3 organotin catalysts continuation reactions then and carried out dealcoholization in 58 hours. reaction is mixed clear liquid add the polymkeric substance that settles out in 150 milliliters of sherwood oils, molten again in tetrahydrofuran (THF) the gained white solid, in solution, add 0.5 milliliter of trimethylchlorosilane backflow and carried out end-blocking in 5 hours, reaction mixture adds the white polymer of wanting that settles out in 200 milliliters of sherwood oils. get polymkeric substance 1.91 grams. and yield is 70%, this polymkeric substance dissolves in tetrahydrofuran (THF), acetone, toluene equal solvent, light scattering method record molecular weight 6 * 10
5, its tetrahydrofuran solution is used for
29The mensuration of Si-NMR, its peak width at half height Δ
1/2＜1ppm shows that its regularity is fine.
Embodiment 27
The recovery of pre-aminolysis agent PDA is stirred the pre-proper amount of sodium hydroxide strong solution of para-phenylene diamine dihydrochloride of filtering gained 0.5 hour in 0 ℃, leaves standstill, and filter and obtain the Ursol D crude product, dry final vacuum distillation under nitrogen protection, its vacuum tightness is 10
-3～20mmHg, temperature is 50～150 ℃, obtains white and light yellow crystal, fusing point 144.5-145.5 ℃, yield 95%.
Claims (13)
1. trapezoidal organic poly sesquisiloxane, its structure as shown in the formula:
In the formula: R is alkyl, alkyl, aryl or the derivative that contains these groups;
N is the integer greater than 1;
Its side group has following structure:
(A) having π-π aryl piles up: the condensed-nuclei aromatics of phenyl, naphthyl, benzo phenanthryl and corresponding derivative;
Containing electronics to give-group of receptor acting, is phenol, ether, alcohol, amine, naphthalene, anthracene or luxuriant and rich with fragrance fragrant condensed ring thing to body wherein; Acceptor is alkene, quinone derivative or the fragrance derivatives of haloalkane, band negative group;
The side group of hydrophobic type effect: the different alkyl chain or derivatives thereofs of length;
(B) have hydrogen bond type side group template, comprising:
Alcoholic extract hydroxyl group, phenolic hydroxyl group, urea groups, amido formate base and aliphatic amide, aromatic amide or derivatives thereof.
2. the trapezoidal organic poly sesquisiloxane of claim 1 is characterized in that, described alkyl is saturated or unsaturated alkyl or halo, hydroxyl generation, ammonia (amine) base generation, carbonyl or epoxy group(ing) substituted hydrocarbon radical.
3. the trapezoidal organic poly sesquisiloxane of claim 1 is characterized in that, n=10-500.
4. the described trapezoidal organic poly sesquisiloxane method of preparation claim 1 adopts ladder support template, and key step is:
A) concentration of chlorosilane solution adding calculated amount is the 2-10g/100ml absorption agent, and in-50 to 10 ℃ stir, and adding concentration is the pre-aminolysis agent solution of 2-10g/100ml, reacts 0.5-2 hour;
B) add the diluent water of calculated amount, this diluent water concentration is 10-25ml water/100ml, stirs 1-6 hour under the room temperature, filters, and filtrate is used anhydrous sodium sulfate drying, gets supernatant liquor and carries out end-blocking with the trimethylchlorosilane of calculated amount;
C) add the water and the catalyzer of calculated amount, the ratio 0.01～1/1 of catalyzer and water wherein, room temperature to 60 ℃ stirred 20-50 hour down; Saturated sodium-chloride water solution is washed neutrality, and anhydrous sodium sulfate drying obtains the clear solution of trapezoidal organic poly sesquisiloxane;
In the above-mentioned reaction:
Used solvent is aromatic hydrocarbons, naphthenic hydrocarbon and derivative thereof, and structure is:
R is: hydrogen, halogen, alkyl, ester cyclic group, nitro or cyano group;
Absorption agent is triethylamine or pyridine;
Trichlorosilane is 2: 1 with the mol ratio of pre-aminolysis agent;
Pre-aminolysis agent comprises:
I) aliphatic alpha, ω-di-primary amine and have and draw the electron substituent group derivative to what its hydrogen bond template did not have a destruction, structure is:
R wherein
1, R
2, R
3Be respectively H or draw electron substituent group, x=0,1,2,3...＜5 integers;
Ii) 1,4-Ursol D and having for 1, the hydrogen bond template of 4-Ursol D does not have the electron substituent group that draws of destruction, and structure is:
R wherein
1, R
2, R
3, R
4Be respectively H or electron substituent group;
Iii) right-aryl diamine class and do not have for what the hydrogen bond template of aryl diamine is had a destruction and draw the electron substituent group derivative, structure is:
Wherein R ' represention oxygen atom, alkylidene group-(CH
2)
n-, wherein n=0,1,2,3.....＜5 integers, thiazolinyl, alkynyl or contain groups such as substituent alkylidene group; R
1, R
2, R
3, R
4Be respectively H or draw electron substituent group;
Drawing electron substituent group is halogen, carbonyl, ester group, nitro, cyano group, thiazolinyl, alkynyl or aryl;
Diluent water is the ketone of water and following structure or the mixing solutions of ether compound:
The mol ratio of trimethylchlorosilane and trichlorosilane is 3 * 10
-1To 7 * 10
-1/ 1;
Catalyzer is: protonic acid, alkali, organic acid, organic bases or metal oxide.
5. the preparation method of claim 4 is characterized in that, ketone in the diluent water or ether compound are that acetone, dioxane or four furan hydrogen are muttered.
6. the preparation method of claim 4 is characterized in that, the temperature among the step a is-30 to-5 ℃.
7. claim 4 or 6 preparation method is characterized in that the temperature among the step a is-15 to 10 ℃.
8. the described trapezoidal organic poly sesquisiloxane method of preparation claim 1 adopts aryl accumulation type side group template, and key step is:
Under the argon shield, adding concentration in the 2mmol coupling agent is the toluene of 0.05～0.2g/mL or the sily oxide coupling agent 1mmol of tetrahydrofuran solvent and equivalent, 70 to 100 ℃ were reacted 48～120 hours down, except that after desolvating, 0 to 30 ℃ down with the tetrahydrofuran (THF) of volume ratio 10/1/aqueous solution 50-100ml hydrolysis 10-20 hour, wherein drip 2-3 in tetrahydrofuran (THF)/aqueous solution and drip 1M hydrochloric acid, be washed to neutrality; Use the siccative drying, filter, solid is through recrystallization purifying; Add concentration and be the phenyl ether of 0.3～1g/mL or tetrachloroethane 20-50mL and with the catalyzer of reactant quality than 0.5-1%, decompression, 60 to 200 ℃ of temperature of reaction, 24～48 hours reaction times; Remove the follow-up continuous decompression of desolvating, carry out solid state polymerization; Polymerisate is dissolved in the sherwood oil, is that 1: 1 methanol/ethanol precipitation obtains the solid trapezoidal organic poly sesquisiloxane through volume ratio;
Used catalyzer is: organic amine compound, mineral acid or organic acid compound.
9. the preparation method of claim 8 is characterized in that, the organic amine compound in the catalyst system therefor is triethylamine, Tributylamine, tetrabutylammonium hydroxide phosphine or tetramethyl-oxyammonia.
10. the described trapezoidal organic poly sesquisiloxane method of preparation claim 1 adopts hydrogen bond type side group template, and key step is:
With concentration is that the coupling silicon monomer solution of 2～8g/100mL adds in the chlorobenzene, adds 2-3 under the room temperature and drips the diluent water that adds calculated amount behind the vitriol oil, and this diluent water concentration is 10-25ml water/100ml, reacts 30-50 hour; Add the triethylamine with vitriol oil equivalent, remove by filter the salt of generation; Add 3-4 and drip dibutyl tin laurate, room temperature to 50 ℃ reaction 48-60 hour; Add petroleum ether precipitation and go out solid, the gained solid is dissolved in the tetrahydrofuran (THF), adding excessive trimethylchlorosilane a few hours of refluxing carries out end capping, adds petroleum ether precipitation, obtains the solid trapezoidal organic poly sesquisiloxane;
Used coupling silicon monomer is two hydrogen bond template side group four alkoxyl group sily oxide;
Used catalyzer is an organotin.
11. the preparation method of claim 10 is characterized in that, catalyzer is a dibutyl tin dilaurate.
12. the preparation method of claim 8 or 10 is characterized in that, selects to have the polar solvent in the aryl accumulation type side group template, to strengthen its template action and guarantee to carry out polymerization under homogeneous system; Select polarity low, water insoluble in the hydrogen bond type side group template, and the hydro carbons or derivatives thereof that does not react with the required catalyzer of preparation and silicon monomer and reaction intermediate thereof.
13. the preparation method of claim 12 is characterized in that, described hydro carbons and derivative thereof are that alkane, unsaturated olefin, alkynes, aromatic hydrocarbons and halo thereof, carbonyl generation, nitroaromatic, cyano group are for compound.
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