CN1280995A - Trapezoidal polysiloxane containing organic bridge radical and its preparing process - Google Patents
Trapezoidal polysiloxane containing organic bridge radical and its preparing process Download PDFInfo
- Publication number
- CN1280995A CN1280995A CN 99109826 CN99109826A CN1280995A CN 1280995 A CN1280995 A CN 1280995A CN 99109826 CN99109826 CN 99109826 CN 99109826 A CN99109826 A CN 99109826A CN 1280995 A CN1280995 A CN 1280995A
- Authority
- CN
- China
- Prior art keywords
- solution
- reaction
- organic abutment
- organosilane monomer
- abutment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
A ladder polysiloxane containing organic bridged radical is prepared through three steps of monomer synthesis, monomer hydrolysis and condensation. The organosilicon omnomer containing organic bridged radical is prepared by Grignard reaction or addition reaction of silicon and hydrogen. Selecting different bridged radicals can obtain different sizes of ladder frame and different chemical affinities. Said ladder polysiloxane has structural normelization up to 80-100%, molecular weight of 5000-7000000 and ladder frame size of 5-30A, and can be widely used for hybridized organic/inorganic material, high-molecular tubular organosilicon material and supermolecular composite material.
Description
The present invention relates to a kind of ladder polysiloxane, particularly a kind of ladder polysiloxane that contains organic abutment and preparation method thereof.
Nineteen sixty Brown, J.F. (J.Am.Chem.SOC., 1960,82,6194) reported first is phenyl triethoxysilane pyrohydrolysis condensation prepared trapezoidal polyphenyl base silsesquioxane (Ph-T), but the Ph-T regularity that makes with this method is low, and more branching is arranged, and reaction conditions is extremely harsh, can't be used for preparing the siloxanes that contains active group.￡ 1989 and nineteen ninety Schunichiro, U. (EP 312280, and JP 02 105881) has reported the trapezoidal polyhydric sesquisiloxane (H-T) of hydroxyl end socket, but does not report the data of its regularity of any sign and other configuration aspects.1994 Chinese patent (CN 9410050) " the trapezoidal poly-hydrogen base silsesquioxane of high regularity and multipolymer thereof and their method for making " disclosed and Japanese Patent (JP08,188649) disclose " being with the trapezoidal polysilsesquioxane and the manufacture method thereof of solubility and film-forming properties ".(React.Polym. in 1999,1999,39,1) reported synthesizing and sign of active trapezoidal polyvinyl silsesquioxane and polypropylene-base silsesquioxane again, this preparation method's reaction conditions gentleness is suitable for preparing nonactive and active trapezoidal polysilsesquioxane, but because the abutment of this kind ladderlike polymer is a fixed Si-O-Si bridge, its abutment size is little, and chemical affinity is restricted, is difficult to freely regulate and control the size and the chemical affinity of abutment.
It is little that purpose of the present invention has overcome the abutment size, restricted and synthetic a kind of abutment size of chemical affinity and chemical affinity can freely be regulated and control as required, and have the novel ladder polysiloxane that contains organic abutment of high compound with regular structure and good solubility.
A kind of ladder polysiloxane regularity that contains organic abutment of the present invention reaches 80-100%, and molecular weight ranges is 5 * 10
3-7 * 10
6, terraced frame size range is 5-30 , general structure is as follows:
In the formula: n is 10-10
5Integer, R is a hydrogen atom; Ester group; Alkyl; Substituted alkyl; Thiazolinyl; Substituted alkenyl; Alkynyl; Substituted alkynyl; Aryl or substituted aryl.In the formula
Represent organic abutment, its structure is following 13 kinds:
A kind of preparation method who contains the ladder polysiloxane of organic abutment of the present invention, step is carried out in the following order:
(1) contain organosilane monomer synthetic of organic abutment: be that addition reaction of silicon with hydrogen by chlorosilane or organoalkoxysilane obtains, reaction is that step is carried out in the following order:
To contain the compound of end thiazolinyl or Terminal Acetylenes base or contain and hold the silane of thiazolinyl or Terminal Acetylenes base to be dissolved in the tetrahydrofuran solution, under argon shield, platinum catalyst be injected.Stirred at ambient temperature 30 minutes, and then the silane of siliceous hydrogen base or the compound of siliceous hydrogen base were added reaction system, above-mentioned two kinds of material molar ratios are 2: 1-4: 1.Reaction mixture made the organosilane monomer that contains organic abutment in 24-48 hour 40 ℃ of reactions, and its structural formula is following 13 kinds:
Wherein: R is a hydrogen atom; Ester group; Alkyl; Substituted alkyl; Thiazolinyl; Substituted alkenyl; Alkynyl; Substituted alkynyl; Aryl or substituted aryl, R ' be X (X=Cl, Br, I) or alkoxyl group.(2) hydrolysis reaction: (I). be that the above-mentioned organosilane monomer that contains organic abutment is dissolved in volume ratio is 1.5: 1-4: in 1 the toluene acetone mixed solvent, concentration is 0.05-0.3mmol/mL, (II) under the ice-water bath condition is that 1: 50 water and acetone mixing solutions are added drop-wise in the above-mentioned monomer solution and make it complete hydrolysis with volume ratio, water and monomeric mol ratio are 4: 1, (III) at room temperature continues to stir 3-6 hour, (3) condensation reaction, promptly in said hydrolyzed solution, add the vitriol oil or triethylamine catalyzer, add anhydrous sodium sulphate again, being warmed up to 50 ℃ then stirred 2-5 days, solution water is washed till neutrality, add anhydrous sodium sulphate as water-retaining agent, be warmed up to 40-60 ℃ then and stirred 2-5 days.(4) end-blocking and purifying
To be washed till neutrality by the condensation product solution water that step 3 makes, and add anhydrous sodium sulphate and remove moisture in the solution, add pyridine then therein.Under induction stirring, be that the toluene solution of the trimethylchlorosilane of 0.1mol/L is added drop-wise in the condensation product solution with concentration in room temperature.Continue to stir 8 hours in room temperature again after dropwising.At last solution water is washed till neutrality, adds anhydrous sodium sulphate and dewater and make the ladder polysiloxane that contains organic abutment.This step also can add MM acid by the equilibration reaction end socket.
Of the present inventionly utilize addition reaction of silicon with hydrogen to prepare to contain the platinum catalyst of the organosilane monomer of organic abutment to be Platinic chloride or Dicyclopentadiene (DCPD) platinum dichloride.
The organosilane monomer that utilizes addition reaction of silicon with hydrogen to prepare to contain organic abutment of the present invention platinum catalyst be 1-10mg/mL with the mol ratio that contains end thiazolinyl or Terminal Acetylenes based compound.
Contain the end thiazolinyl among the preparation method of the organosilane monomer that utilizes addition reaction of silicon with hydrogen to prepare to contain organic abutment of the present invention or the Terminal Acetylenes based compound is following 10 kinds:
The compound of siliceous hydrogen base is following four kinds among the preparation method of the organosilane monomer that utilizes addition reaction of silicon with hydrogen to prepare to contain organic abutment of the present invention:
A kind of preparation method who contains the ladder polysiloxane of organic abutment of the present invention; step is carried out in the following order: (1) contains organosilane monomer synthetic of organic abutment: be that grignard reaction by chlorosilane or organoalkoxysilane and Grignard reagent obtains; reaction is that step is carried out in the following order: (I) is under argon shield; with concentration is that the two halid tetrahydrofuran solution of 0.2-0.8mmol/mL is added drop-wise in the tetrahydrofuran solution of magnesium that concentration is 10%-50%; magnesium is 2.0 with two halid mol ratios: 1-4: 1; reaction system stirred 1 hour at reflux state; (II) is under reflux state; above-mentioned drips of solution is added in the tetrahydrofuran solution of trichlorosilane or trialkoxy silane; trichlorosilane or trialkoxy silane and two halid mol ratio are 4: 1-12: 1; after dropwising; solution stirred 1-5 hour at reflux state; (III) drains tetrahydrofuran solvent; add the salt that the normal hexane precipitation generates; collect supernatant liquid; make the organosilane monomer that contains organic abutment through underpressure distillation or post separation, its structural formula is following four kinds:
Wherein: R is a hydrogen atom; Ester group; Alkyl; Substituted alkyl; Thiazolinyl; Substituted alkenyl; Alkynyl; Substituted alkynyl; Aryl or substituted aryl, R ' be X (X=Cl, Br, I) or alkoxyl group.(2) hydrolysis reaction: (I). be that the above-mentioned organosilane monomer that contains organic abutment is dissolved in volume ratio is 1.5: 1-4: in 1 the toluene acetone mixed solvent, concentration is 0.05-0.3mmol/mL, (II) under the ice-water bath condition is that 1: 50 water and acetone mixing solutions are added drop-wise in the above-mentioned monomer solution and make it complete hydrolysis with volume ratio, water and monomeric mol ratio are 4: 1, (III) at room temperature continues to stir 3-6 hour, (3) condensation reaction, promptly in said hydrolyzed solution, add the vitriol oil or triethylamine catalyzer, add anhydrous sodium sulphate again, being warmed up to 50 ℃ then stirred 2-5 days, solution water is washed till neutrality, add anhydrous sodium sulphate as water-retaining agent, be warmed up to 40-60 ℃ then and stirred 2-5 days.(4) end-blocking and purifying
To be washed till neutrality by the condensation product solution water that step 3 makes, and add anhydrous sodium sulphate and remove moisture in the solution, add pyridine then therein.Under induction stirring, be that the toluene solution of the trimethylchlorosilane of 0.1mol/L is added drop-wise in the condensation product solution with concentration in room temperature.Continue to stir 8 hours in room temperature again after dropwising.At last solution water is washed till neutrality, adds anhydrous sodium sulphate and dewater and make the ladder polysiloxane that contains organic abutment.This step also can add MM acid by the equilibration reaction end socket.
Two halogenide that the grignard reaction that utilizes chlorosilane or organoalkoxysilane and Grignard reagent of the present invention prepares the organosilane monomer that contains organic abutment are following four kinds:
Alkoxyl group is methoxy or ethoxy in the structural formula of the organosilane monomer that contains organic abutment that the grignard reaction that utilizes chlorosilane or organoalkoxysilane and Grignard reagent of the present invention prepares.
Closure agent trimethylchlorosilane used among the preparation method of a kind of ladder polysiloxane that contains organic abutment of the present invention is 1 * 10 with the mol ratio that contains the organosilane monomer of organic abutment
-1-1 * 10
-7
The salient features of a kind of ladder polysiloxane that contains organic abutment of the present invention is as shown in table 1.
Table 1 contains the salient features of the ladder polysiloxane of organic abutment
| Project | The ladder polysiloxane that contains organic abutment |
| Ladder frame size () | ????5-30 |
| Chemical affinity | Can between wetting ability and lipophilicity, regulate |
| Outward appearance | The water white transparency solid |
| Solvability | Be dissolved in the organic solvents such as toluene, tetrahydrofuran (THF), acetone, methylene dichloride |
| Molecular weight (GPC survey) | ????5×10 3-7×10 6 |
| Productive rate (%) | ????70-95 |
| Regularity (%) | ????80-100 |
A kind of ladder polysiloxane that contains organic abutment of the present invention has high compound with regular structure, terraced frame size adjustable, chemical affinity adjustability and good solubility.It has broad application prospects in organic/inorganic hybridization material, nonlinear optical material, tubular organosilicon polymer material and fields such as supramolecule matrix material and electronic material thereof.
Embodiment 1:
In the reaction flask of 250mL, add 3.4g (13.8mol) 1,4-phenyl dicarbapentaborane-two (1-propenyl) ether, the applying argon gas displacement three times of then system being found time.Under argon shield and induction stirring; 30mL tetrahydrofuran solvent and 3mL (M=1mg/mL) Dicyclopentadiene (DCPD) platinum dichloride catalyzer are injected reaction flask; stirring at room 30 minutes; then 2.4g (30.4mol) methyl hydrogen dichlorosilane is injected reaction flask; in 40 ℃ of reactions 24 hours, at last solvent and unreacted reactant are taken out 6.52g (13.7mmol) target monomer.It is in 4: 1 the toluene acetone mixed solvent that above-mentioned monomer is dissolved in the 45ml volume ratio, under the ice-water bath condition 1mL (54.8mmol) water and 30mL acetone mixed solution is added drop-wise in the monomer solution in 6 hours then, continues to stir 3-6 hour in room temperature again.Take acetone solvent away, add 5 vitriol oils and a small amount of anhydrous sodium sulphate, be warmed up to 50-60 ℃ and stirred 72 hours.Again condensation product is washed to neutrality, adds anhydrous sodium sulfate drying and spend the night.Toluene solution 20mL with 0.02g (0.18mmol) trimethylchlorosilane was added drop-wise in the solution of condensation product in 3 hours then.Add 14.2mg (0.18mmol) pyridine in the condensation product solution as acid absorber.Dropwising the back continues to stir 8 hours in room temperature.At last solution water is washed till neutrality, adds anhydrous sodium sulfate drying and dewater, get water white transparency-(CH
2)
3OCOC
6H
4COO (CH
2)
3The toluene solution of-abutting ladder poly polymethyl siloxane, its concentration are 57mg/mL, productive rate 95%.It is 2.7 * 10 that the GPC method is surveyed molecular weight
4,
29It is 100% that Si-NMR surveys regularity.
Embodiment 2:
Device and the operating process same with synthesis example 1 are used diethynylbenzene is replaced 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with phenyl hydrogen dichlorosilane, makes water white transparency-CH=CHC
6H
4The toluene solution of CH=CH-abutting ladder poly phenyl silicone, its concentration are 52mg/mL, productive rate 94%.It is 4.8 * 10 that the GPC method is surveyed molecular weight
5,
29It is 94% that Si-NMR surveys regularity.
Embodiment 3:
Device and the operating process same with synthesis example 1 are used alkynes propoxy-benzene is replaced 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with chloropropyl hydrogen dichlorosilane, makes water white transparency-CH=CHCH
2OC
6H
4OCH
2The toluene solution of CH=CH-abutting ladder poly polychlorostyrene propyl-siloxane, its concentration is 37mg/mL, productive rate 88%.It is 7.0 * 10 that the GPC method is surveyed molecular weight
6,
29It is 97% that Si-NMR measures its regularity.
Embodiment 4:
Device and the operating process same with synthesis example 1 are used the alkynes butyl phenyl ether is replaced 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with phenyl hydrogen dichlorosilane, makes water white transparency-CH=CH (CH
2)
2OC
6H
4O (CH
2)
2The toluene solution of CH=CH-abutting ladder poly phenyl silicone, its concentration are 59mg/mL, productive rate 95%.It is 5.0 * 10 that the GPC method is surveyed molecular weight
3,
29It is 87% that Si-NMR measures its regularity.
Embodiment 5:
Device and the operating process same with synthesis example 1, with 1,4-phenyl dicarbapentaborane-two (1-pentenyl) ether replaces 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with ethyl hydrogen dichlorosilane, makes water white transparency-(CH
2)
5OCOC
6H
4COO (CH
2)
5The toluene solution of the poly-ethylsiloxane of-abutting ladder poly, its concentration is 62mg/mL, it is 8.0 * 10 that productive rate 94%.GPC method is surveyed molecular weight
5,
29It is 92% that Si-NMR measures its regularity.Embodiment 6:
Device and the operating process same with synthesis example 1, with 4,4 '-hexichol ether dicarbapentaborane-two (1-proyl) ether replaces 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with phenyl hydrogen dichlorosilane, makes water white transparency-CH=CHCH
2OCOC
6H
4COOCH
2The toluene solution of CH=CH-abutting ladder poly phenyl silicone, its concentration are 56mg/mL, productive rate 89%.It is 8.0 * 10 that the GPC method is surveyed molecular weight
4,
29It is 89% that Si-NMR measures its regularity.
Embodiment 7:
Device and the operating process same with synthesis example 1 replace 1 with 2,2 '-two (allyl phenyl) propane, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with xenyl hydrogen dichlorosilane, makes water white transparency-(CH
2)
3C
6H
4(CH
3) C (CH
3) C6H
4(CH
2)
3The toluene solution of the poly-xenyl siloxanes of-abutting ladder poly, its concentration is 46mg/mL, productive rate 89%.It is 5.8 * 10 that the GPC method is surveyed molecular weight
5,
29It is 90% that Si-NMR measures its regularity.
Embodiment 8:
Device and the operating process same with synthesis example 1, with 4,4 '-the diallyl phenyl ether replaces 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether makes water white transparency-(CH
2)
3C
6H
4OC
6H
4(CH
2)
3The toluene solution of-abutting ladder poly polymethyl siloxane, its concentration are 37mg/mL, productive rate 95%.It is 9.7 * 10 that the GPC method is surveyed molecular weight
3,
29It is 83% that Si-NMR measures its regularity.
Embodiment 9:
Device and the operating process same with synthesis example 1 are used diacetylene biphenyl is replaced 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with rubigan hydrogen dichlorosilane, makes water white transparency-CH=CHC
6H
4C
6H
4The toluene solution of CH=CH-abutting ladder poly polychlorostyrene phenyl siloxane, its concentration is 52mg/mL, productive rate 91%.It is 5.7 * 10 that the GPC method is surveyed molecular weight
4,
29It is 93% that Si-NMR measures its regularity.
Embodiment 10:
Device and the operating process same with synthesis example 1 are used divinylbenzene is replaced 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether makes water white transparency-(CH
2)
2C
6H
4(CH
2)
2The toluene solution of-abutting ladder poly polymethyl siloxane, its concentration are 45mg/mL, productive rate 70%.It is 9.2 * 10 that the GPC method is surveyed molecular weight
4,
29It is 86% that Si-NMR measures its regularity.Embodiment 11:
Device and the operating process same with synthesis example 1 are used divinyl biphenyl is replaced 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with ethyl hydrogen dichlorosilane, makes water white transparency-(CH
2)
2C
6H
4C
6H
4(CH
2)
2The toluene solution of the poly-ethylsiloxane of-abutting ladder poly, its concentration is 40mg/mL, productive rate 79%.It is 3.8 * 10 that the GPC method is surveyed molecular weight
5,
29It is 84% that Si-NMR measures its regularity.
Embodiment 12:
Device and the operating process same with synthesis example 1 are used the divinyl terphenyl is replaced 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with phenyl hydrogen dichlorosilane, makes water white transparency-(CH
2)
2C
6H
4C
6H
4C
6H
4(CH
2)
2The toluene solution of-abutting ladder poly phenyl silicone, its concentration are 52mg/mL, productive rate 88%.It is 6.7 * 10 that the GPC method is surveyed molecular weight
5,
29It is 94% that Si-NMR measures its regularity.
Embodiment 13:
Device and the operating process same with synthesis example 1, with 1,4-phenyl dicarbapentaborane-divinyl ether replaces 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with phenyl hydrogen dichlorosilane, makes water white transparency-(CH
2)
2OCOC
6H
4COO (CH
2)
2The toluene solution of-abutting ladder poly phenyl silicone, its concentration are 39mg/mL, productive rate 85%.It is 3.6 * 10 that the GPC method is surveyed molecular weight
5,
29It is 85% that Si-NMR measures its regularity.
Embodiment 14:
Device and the operating process same with synthesis example 1 replace 1 with allyloxy benzene, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with chloroethyl hydrogen dichlorosilane, makes water white transparency-(CH
2)
3OC
6H
4O (CH
2)
3The toluene solution of-abutting ladder poly polychlorostyrene ethylsiloxane, its concentration are 47mg/mL, productive rate 89%.It is 3.2 * 10 that the GPC method is surveyed molecular weight
6,
29It is 95% that Si-NMR measures its regularity.
Embodiment 15:
Device and the operating process same with synthesis example 1 replace 1 with two [right-(dimethyl is silica-based) phenyl] ether, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with chloroethyl vinyl dichlorosilane, makes water white transparency-(CH
2)
2Si (CH
3)
2C
6H
4OC
6H
4(CH
3)
2Si (CH
2)
2The toluene solution of-abutting ladder poly polychlorostyrene ethylsiloxane, its concentration are 44mg/mL, productive rate 85%.It is 6.1 * 10 that the GPC method is surveyed molecular weight
6,
29It is 93% that Si-NMR measures its regularity.Embodiment 16:
Device and the operating process same with synthesis example 1 replace 1 with two [right-(dimethyl is silica-based) phenyl] ether, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with ethyl propionate base propenyl dichlorosilane, makes water white transparency-(CH
2)
3Si (CH
3)
2C
6H
4OC
6H
4(CH
3)
2Si (CH
2)
3The toluene solution of the poly-ethyl propionate radical siloxane of-abutting ladder poly, its concentration is 51mg/mL, productive rate 83%.It is 3.5 * 10 that the GPC method is surveyed molecular weight
6,
29It is 86% that Si-NMR measures its regularity.
Embodiment 17:
Device and the operating process same with synthesis example 1, with 1,4-two (dimethyl-silicon methyl) benzene replaces 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with chloroethyl vinyl dichlorosilane, makes water white transparency-(CH
2)
2Si (CH
3)
2CH
2C
6H
4CH
2(CH
3)
2Si (CH
2)
2The toluene solution of-abutting ladder poly polychlorostyrene ethylsiloxane, its concentration are 45mg/mL, productive rate 89%.It is 7.5 * 10 that the GPC method is surveyed molecular weight
4,
29It is 92% that Si-NMR measures its regularity.
Embodiment 18:
Device and the operating process same with synthesis example 1, with 1,4-two (dimethyl-silicon methyl) benzene replaces 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether with two (chlorallylene base) dichlorosilane replacement methyl hydrogen dichlorosilane, makes water white transparency-(CH
2)
3Si (CH
3)
2CH
2C
6H
4CH
2(CH
3)
2Si (CH
2)
3The toluene solution of the poly-chlorallylene radical siloxane of-abutting ladder poly, its concentration is 34mg/mL, productive rate 95%.It is 6.5 * 10 that the GPC method is surveyed molecular weight
5,
29It is 90% that Si-NMR measures its regularity.
Embodiment 19:
Device and the operating process same with synthesis example 1, with 1,4-two (dimethyl is silica-based) benzene replaces 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether with two proyl dichlorosilanes replacement methyl hydrogen dichlorosilane, makes water white transparency-(CH
2)
2Si (CH
3)
2C
6H
4(CH
3)
2Si (CH
2)
2The toluene solution of the poly-proyl siloxanes of-abutting ladder poly, its concentration is 48mg/mL, productive rate 92%.It is 8.7 * 10 that the GPC method is surveyed molecular weight
5,
29It is 84% that Si-NMR measures its regularity.
Embodiment 20:
Device and the operating process same with synthesis example 1, with 1,4-two (dimethyl is silica-based) benzene replaces 1, and 4-phenyl dicarbapentaborane-two (1-propenyl) ether replaces methyl hydrogen dichlorosilane with 3-chloroallylene base proyl dichlorosilane, makes water white transparency-(CH
2)
3Si (CH
3)
2C
6H
4(CH
3)
2Si (CH
2)
3The toluene solution of the poly-3-chloroallylene radical siloxane of-abutting ladder poly, its concentration is 40mg/mL, productive rate 90%.It is 2.7 * 10 that the GPC method is surveyed molecular weight
6,
29It is 93% that Si-NMR measures its regularity.
Embodiment 21:
Under argon shield and induction stirring, the tetrahydrofuran solution 40mL of 4.72g (0.02mol) paradibromobenzene is added drop-wise in the 100mL tetrahydrofuran solution that contains 1.06g (0.044mol) magnesium chips.Reaction system was stirred 1 hour at reflux state.Then above-mentioned drips of solution is added in the 100mL tetrahydrofuran solution that contains 17.80g (0.1mol) Union carbide A-162.After dripping, system continues to stir 4 hours at reflux state, then tetrahydrofuran solvent is drained, and filters out salt, adds 400mL normal hexane deposited salt again in filtrate.Collect supernatant liquid and normal hexane that will be wherein and excessive Union carbide A-162 and take out, get 1 through underpressure distillation, 4-penylene-two (methyl, diethoxy) silane monomer 4.48g (0.013mol), yield 45%.It is in 4: 1 the toluene acetone mixed solvent that above-mentioned monomer is dissolved in the 45ml volume ratio, then 0.94mL (0.052mol) water and 30mL acetone mixed solution is added drop-wise in the monomer solution in 6 hours.Take acetone solvent away, add 5 vitriol oils and a small amount of anhydrous sodium sulphate, be warmed up to 50-60 ℃ and stirred 72 hours.Again condensation product is washed to neutrality, adds anhydrous sodium sulfate drying and spend the night.Toluene solution 20mL with 0.02g (0.18mmol) trimethylchlorosilane was added drop-wise in the solution of condensation product in 3 hours then.Add 14.2mg (0.18mmol) pyridine in the condensation product solution as acid absorber.Dropwising the back continues to stir 8 hours in room temperature.At last solution water is washed till neutrality, adds anhydrous sodium sulfate drying and spend the night, get the toluene solution of water white transparency benzene abutting ladder poly polymethyl siloxane, its concentration is 25mg/mL, productive rate 80%.It is 7.6 * 10 that the GPC method is surveyed molecular weight
4,
29It is 90% that Si-NMR measures its regularity.
Embodiment 22:
Device and the operating process same with synthesis example 1 replace Union carbide A-162 with hydrogen ethyl triethoxy silicane alkane, and making concentration is the poly-hydrogen radical siloxane water white transparency toluene solution of benzene abutting ladder poly of 28mg/mL.Productive rate 85%.It is 5.6 * 10 that the GPC method is surveyed molecular weight
4 29It is 96% that Si-NMR measures its regularity.
Embodiment 23:
Device and the operating process same with synthesis example 1, with '-dibromobiphenyl is replaced paradibromobenzene, replace Union carbide A-162 with vinyl trichloro silane, get the toluene solution of water white transparency biphenyl abutting ladder poly polyvinyl siloxane, its concentration is 56mg/mL, productive rate 87%.It is 2.7 * 10 that the GPC method is surveyed molecular weight
5,
29It is 85% that Si-NMR measures its regularity.
Embodiment 24:
Device and the operating process same with synthesis example 1, with the dibromo terphenyl is replaced paradibromobenzene, replace Union carbide A-162 with vinyltrimethoxy silane, get the toluene solution of water white transparency terphenyl abutting ladder poly polyvinyl siloxane, its concentration is 48mg/mL, productive rate 89%.It is 1.4 * 10 that the GPC method is surveyed molecular weight
5,
29It is 83% that Si-NMR measures its regularity.
Embodiment 25:
Device and the operating process same with synthesis example 1 are used xylene dichloride is replaced paradibromobenzene, replace Union carbide A-162 with the proyl Trimethoxy silane, water white transparency-CH
2C
6H
4CH
2The toluene solution of the poly-proyl siloxanes of-abutting ladder poly, its concentration is 54mg/mL, productive rate 93%.It is 7.4 * 10 that the GPC method is surveyed molecular weight
4,
29It is 90% that Si-NMR measures its regularity.
Embodiment 26:
Device and the operating process same with synthesis example 1, with 4,4 '-the diiodo-dimethyl diphenyl is replaced paradibromobenzene, replace Union carbide A-162 with the xenyl Trimethoxy silane, water white transparency-CH
2C
6H
4C
6H
4CH
2The toluene solution of the poly-xenyl siloxanes of-abutting ladder poly, its concentration is 35mg/mL, productive rate 90%.It is 7.1 * 10 that the GPC method is surveyed molecular weight
5,
29It is 92% that Si-NMR measures its regularity.
Embodiment 27:
Device and the operating process same with synthesis example 1, with 4,4 '-diiodo-dimethyl terphenyl is replaced paradibromobenzene, replace Union carbide A-162 with ethyl trichlorosilane, water white transparency-CH
2C
6H
4C
6H
4C
6H
4CH
2The toluene solution of the poly-ethylsiloxane of-abutting ladder poly, its concentration is 39mg/mL, productive rate 95%.It is 4.7 * 10 that the GPC method is surveyed molecular weight
5,
29It is 87% that Si-NMR measures its regularity.
Embodiment 28:
ClCH is used in device and the operating process same with synthesis example 1
2OC
6H
4OCH
2Cl replaces paradibromobenzene, replaces Union carbide A-162 with the propenyl trichlorosilane, gets water white transparency-CH
2OC
6H
4OCH
2The toluene solution of-abutting ladder poly polypropylene-base siloxanes, its concentration are 42mg/mL, productive rate 93%.It is 6.2 * 10 that the GPC method is surveyed molecular weight
5,
29It is 82% that Si-NMR measures its regularity.
Embodiment 29:
Device and the operating process same with synthesis example 1, with 4,4 '-dibromodiphenyl ether replaces paradibromobenzene, replaces Union carbide A-162 with the propenyl trichlorosilane, water white transparency-C
6H
4OC
6H
4The toluene solution of-abutting ladder poly polypropylene-base siloxanes, its concentration are 58mg/mL, productive rate 86%.It is 3.5 * 10 that the GPC method is surveyed molecular weight
5,
29It is 88% that Si-NMR measures its regularity.
Embodiment 30:
ClCH is used in device and the operating process same with synthesis example 1
2C
6H
4OC
6H
4CH
2Cl replaces paradibromobenzene, replaces Union carbide A-162 with chloropropyl trichloro-silane, gets water white transparency-CH
2C
6H
4OC
6H
4CH
2The toluene solution of-abutting ladder poly polychlorostyrene propyl-siloxane, its concentration are 51mg/mL, productive rate 90%.It is 2.9 * 10 that the GPC method is surveyed molecular weight
6,
29It is 91% that Si-NMR measures its regularity.
Embodiment 31:
Device and the operating process same with synthesis example 1 replace paradibromobenzenes with 2,2 '-two pairs of bromophenyl propane, replace Union carbide A-162 with 3-chloroallylene base trichlorosilane, water white transparency-C
6H
4(CH
3)
2CC
6H
4The toluene solution of the poly-3-chloroallylene radical siloxane of-abutting ladder poly, its concentration is 50mg/mL, productive rate 92%.It is 4.1 * 10 that the GPC method is surveyed molecular weight
6,
29It is 95% that Si-NMR measures its regularity.
Embodiment 32:
Device and the operating process same with synthesis example 1 replace paradibromobenzene with 2,2 '-two para-bromo toluene base propane, replace Union carbide A-162 with 3-chloroallylene base trichlorosilane, water white transparency-CH
2C
6H
4(CH
3)
2CC
6H
4CH
2The toluene solution of the poly-3-chloroallylene radical siloxane of-abutting ladder poly, its concentration is 45mg/mL, productive rate 82%.It is 4.5 * 10 that the GPC method is surveyed molecular weight
5,
29It is 92% that Si-NMR measures its regularity.
Claims (10)
1. a ladder polysiloxane that contains organic abutment is characterized in that regularity reaches 80-100%, and molecular weight ranges is 5 * 10
3-7 * 10
6, terraced frame size range is 5-30 , this polysiloxane has following structure:
Wherein: n is 10-10
5Integer, R is a hydrogen atom; Ester group; Alkyl; Substituted alkyl; Thiazolinyl; Substituted alkenyl; Alkynyl; Substituted alkynyl; Aryl or substituted aryl,
Represent organic abutment, its structural formula is following 13 kinds:
2. a kind of preparation method who contains the ladder polysiloxane of organic abutment according to claim 1 is characterized in that step is carried out in the following order:
(1) contain organosilane monomer synthetic of organic abutment: be that addition reaction of silicon with hydrogen by chlorosilane or organoalkoxysilane obtains, reaction is that step is carried out in the following order:
To contain the compound of end thiazolinyl or Terminal Acetylenes base or contain holds the silane of thiazolinyl or Terminal Acetylenes base to be dissolved in the tetrahydrofuran solution; under argon shield, platinum catalyst is injected; stirred at ambient temperature 30 minutes; then the silane of siliceous hydrogen base or the compound of siliceous hydrogen base are added reaction system; above-mentioned two kinds of material molar ratios are 2: 1-4: 1. reaction mixture made the organosilane monomer that contains organic abutment in 24-48 hour 40 ℃ of reactions, and its structural formula is following 13 kinds:
Wherein: R is a hydrogen atom; Ester group; Alkyl; Substituted alkyl; Thiazolinyl; Substituted alkenyl; Alkynyl; Substituted alkynyl; Aryl or substituted aryl, R ' be X (X=Cl, Br, I) or alkoxyl group.
(2) hydrolysis reaction: (I). be that the above-mentioned organosilane monomer that contains organic abutment is dissolved in volume ratio is 1.5: 1-4: in 1 the toluene acetone mixed solvent, concentration is 0.05-0.3mmol/mL, (II) under the ice-water bath condition is that 1: 50 water and acetone mixing solutions are added drop-wise in the above-mentioned monomer solution and make it complete hydrolysis with volume ratio, water and monomeric mol ratio are 4: 1, (III) at room temperature continues to stir 3-6 hour
(3) condensation reaction promptly adds the vitriol oil or triethylamine catalyzer in said hydrolyzed solution, add anhydrous sodium sulphate again, is warmed up to 50 ℃ then and stirs 2-5 days, and solution water is washed till neutrality, adds anhydrous sodium sulphate,
(4) end socket reaction, be in above-mentioned solution, to add pyridine as acid absorber, add the toluene solution that concentration is the trimethylchlorosilane of 0.01-0.1mol/L again, the mol ratio of pyridine and trimethylchlorosilane is 1: 1, after reaction finishes solution water is washed till neutrality, makes the ladder polysiloxane colourless transparent solution that contains organic abutment.
3. the preparation method who contains the organosilane monomer of organic abutment according to claim 2 is characterized in that described platinum catalyst is Platinic chloride or Dicyclopentadiene (DCPD) platinum dichloride.
4. the preparation method who contains the organosilane monomer of organic abutment according to claim 2 is characterized in that described platinum catalyst and the mol ratio that contains end thiazolinyl or Terminal Acetylenes based compound are 1-10mg/mL.
5. the preparation method who contains the organosilane monomer of organic abutment according to claim 2 is characterized in that described to contain end thiazolinyl or Terminal Acetylenes based compound be following 10 kinds:
6. the preparation method who contains the organosilane monomer of organic abutment according to claim 2, the compound that it is characterized in that described siliceous hydrogen base is following four kinds:
7. a kind of preparation method who contains the ladder polysiloxane of organic abutment according to claim 1; it is characterized in that step is carried out in the following order: (1) contains organosilane monomer synthetic of organic abutment: be that grignard reaction by chlorosilane or organoalkoxysilane and Grignard reagent obtains; reaction is that step is carried out in the following order: (I) is under argon shield; with concentration is that the two halid tetrahydrofuran solution of 0.2-0.8mmol/mL is added drop-wise in the tetrahydrofuran solution of magnesium that concentration is 10%-50%; magnesium is 2.0 with two halid mol ratios: 1-4: 1; reaction system stirred 1 hour at reflux state; (II) is under reflux state; above-mentioned drips of solution is added in the tetrahydrofuran solution of trichlorosilane or trialkoxy silane; trichlorosilane or trialkoxy silane and two halid mol ratio are 4: 1-12: 1; after dropwising; solution stirred 1-5 hour at reflux state; (III) drains tetrahydrofuran solvent; add the salt that the normal hexane precipitation generates; collect supernatant liquid; make the organosilane monomer that contains organic abutment through underpressure distillation or post separation, its structural formula is following four kinds:
Wherein: R is a hydrogen atom; Ester group; Alkyl; Substituted alkyl; Thiazolinyl; Substituted alkenyl; Alkynyl; Substituted alkynyl; Aryl or substituted aryl, R ' be X (X=Cl, Br, I) or alkoxyl group.(2) hydrolysis reaction: (I). be that the above-mentioned organosilane monomer that contains organic abutment is dissolved in volume ratio is 1.5: 1-4: in 1 the toluene acetone mixed solvent, concentration is 0.05-0.3mmol/mL, (II) under the ice-water bath condition is that 1: 50 water and acetone mixing solutions are added drop-wise in the above-mentioned monomer solution and make it complete hydrolysis with volume ratio, water and monomeric mol ratio are 4: 1, (III) at room temperature continues to stir 3-6 hour, (3) condensation reaction, promptly in said hydrolyzed solution, add the vitriol oil or triethylamine catalyzer, add anhydrous sodium sulphate again, being warmed up to 50 ℃ then stirred 2-5 days, solution water is washed till neutrality, add anhydrous sodium sulphate
(4) end socket reaction, be in above-mentioned solution, to add pyridine as acid absorber, add the toluene solution that concentration is the trimethylchlorosilane of 0.01-0.1mol/L again, the mol ratio of pyridine and trimethylchlorosilane is 1: 1, after reaction finishes solution water is washed till neutrality, makes the ladder polysiloxane colourless transparent solution that contains organic abutment.
8. the preparation method who contains the organosilane monomer of organic abutment according to claim 7 is characterized in that described pair of halogenide is following four kinds:
9. the preparation method who contains the organosilane monomer of organic abutment according to claim 7 is characterized in that the alkoxyl group in the structural formula of the described organosilane monomer that contains organic abutment is a methoxy or ethoxy.
10. according to claim 2 or 7 described a kind of preparation methods that contain the ladder polysiloxane of organic abutment, it is characterized in that described closure agent trimethylchlorosilane and the mol ratio that contains the organosilane monomer of organic abutment are 1 * 10
-1-1 * 10
-7
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109826 CN1280995A (en) | 1999-07-16 | 1999-07-16 | Trapezoidal polysiloxane containing organic bridge radical and its preparing process |
| US09/616,338 US6423772B1 (en) | 1999-07-16 | 2000-07-14 | Organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof, and the method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99109826 CN1280995A (en) | 1999-07-16 | 1999-07-16 | Trapezoidal polysiloxane containing organic bridge radical and its preparing process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1280995A true CN1280995A (en) | 2001-01-24 |
Family
ID=5274179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99109826 Pending CN1280995A (en) | 1999-07-16 | 1999-07-16 | Trapezoidal polysiloxane containing organic bridge radical and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1280995A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270188B (en) * | 2008-05-16 | 2010-11-17 | 太原理工大学 | Method for functionalization of periodic mesoporous organosilicon |
| CN102757781A (en) * | 2011-04-26 | 2012-10-31 | 北京化工大学 | Trapezoidal polysiloxane organic electroluminescent material with pyrene bridge base, and synthesizing method thereof |
| CN103450248A (en) * | 2013-09-13 | 2013-12-18 | 合肥学院 | Preparation method of aromatic ring-containing bridged silsesquioxane monomer |
| CN104045831A (en) * | 2013-03-14 | 2014-09-17 | 中国科学院化学研究所 | Siloxane bridged ladderlike polysiloxane and preparation method thereof |
| CN105585734A (en) * | 2015-12-16 | 2016-05-18 | 东莞兆舜有机硅科技股份有限公司 | 1,2-ditrialkoxy silane crosslinking agent and preparation method and application thereof |
| CN107400238A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院化学研究所 | A kind of multi-arm siloxanes abutting ladder poly-siloxane copolymer and its preparation method and application |
| CN113321935A (en) * | 2021-07-02 | 2021-08-31 | 深圳市泰科科技有限公司 | High-corrosion-resistance silicone rubber material and preparation method thereof |
-
1999
- 1999-07-16 CN CN 99109826 patent/CN1280995A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270188B (en) * | 2008-05-16 | 2010-11-17 | 太原理工大学 | Method for functionalization of periodic mesoporous organosilicon |
| CN102757781A (en) * | 2011-04-26 | 2012-10-31 | 北京化工大学 | Trapezoidal polysiloxane organic electroluminescent material with pyrene bridge base, and synthesizing method thereof |
| CN102757781B (en) * | 2011-04-26 | 2014-03-26 | 北京化工大学 | Trapezoidal polysiloxane organic electroluminescent material with pyrene bridge base, and synthesizing method thereof |
| CN104045831A (en) * | 2013-03-14 | 2014-09-17 | 中国科学院化学研究所 | Siloxane bridged ladderlike polysiloxane and preparation method thereof |
| CN104045831B (en) * | 2013-03-14 | 2016-12-28 | 中国科学院化学研究所 | A kind of siloxanes abutting ladder poly-siloxane and preparation method thereof |
| CN103450248A (en) * | 2013-09-13 | 2013-12-18 | 合肥学院 | Preparation method of aromatic ring-containing bridged silsesquioxane monomer |
| CN105585734A (en) * | 2015-12-16 | 2016-05-18 | 东莞兆舜有机硅科技股份有限公司 | 1,2-ditrialkoxy silane crosslinking agent and preparation method and application thereof |
| CN107400238A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院化学研究所 | A kind of multi-arm siloxanes abutting ladder poly-siloxane copolymer and its preparation method and application |
| CN107400238B (en) * | 2016-05-19 | 2020-05-26 | 中国科学院化学研究所 | Multi-arm siloxane bridged ladder-shaped polysiloxane copolymer and preparation method and application thereof |
| CN113321935A (en) * | 2021-07-02 | 2021-08-31 | 深圳市泰科科技有限公司 | High-corrosion-resistance silicone rubber material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5939576A (en) | Method of functionalizing polycyclic silicones and the compounds so formed | |
| CN1161361C (en) | Cyclic oxosilane | |
| US5942638A (en) | Method of functionalizing polycyclic silicones and the resulting compounds | |
| KR100574573B1 (en) | Carbosiloxane dendrimers | |
| CN1694890A (en) | Alkene-platinum-silyl complexes | |
| Boury et al. | Poly (carbosilane) precursors of silicon carbide: the effect of cross-linking on ceramic residue | |
| EP1268613A2 (en) | Polyorganosilsesquioxane and process for preparing the same | |
| CN1884343A (en) | Novel carborane- (siloxane or silane)- ethinyl high temperature resistant polymer and its preparation method | |
| CN1280995A (en) | Trapezoidal polysiloxane containing organic bridge radical and its preparing process | |
| CN1058730C (en) | High-regularity ladder polyhydric sesquisiloxane and its copolymer and preparing method thereof | |
| JPH06172535A (en) | Preparation of cluster azasilacycloalkyl- functional polysiloxane | |
| Kowalewska et al. | Novel polymer systems with very bulky organosilicon side chain substituents | |
| KR920008123A (en) | Reactive group-containing silicon-based U.A. stabilizer | |
| KR100332466B1 (en) | Multi-reactive polysiloxane compound having halogen substituents and synthetic method thereof | |
| JP2003517072A (en) | Process for producing polyorganosiloxanes by polymerization catalyzed by a catalyst system based on triflic acid or a triflic acid derivative | |
| Allcock et al. | Hybrid phosphazene-organosilicon polymers: II. High-polymer and materials synthesis and properties | |
| CN1133684C (en) | Polysiloxane copolymer with side quarternary ammonium group and its preparation | |
| CN115947750A (en) | Carboxylated silane coupling agent and preparation method thereof | |
| Umezawa et al. | Electroreductive polymerization of mixtures of chloromonosilanes | |
| CN1281661C (en) | Alkynyl-containing poly-siloxane and method for preparing same | |
| CN114746429A (en) | Cyclosilapropane compounds as stable silylene precursors and their use in the catalyst-free preparation of siloxanes | |
| Hengge et al. | Recent advances in the chemistry of cyclopolysilanes | |
| GB2234511A (en) | Electrochemical synthesis of organosilicon compounds | |
| Hengge | New ways to polysilanes | |
| Uhlig | Tailor-made synthesis of functional substituted oligo-and polysilanes from silyl triflates and (aminosilyl) lithium compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |