CN1478805A - Polydisiloxane containing hydrosilicon linkage and its preparation method - Google Patents
Polydisiloxane containing hydrosilicon linkage and its preparation method Download PDFInfo
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- CN1478805A CN1478805A CNA031296955A CN03129695A CN1478805A CN 1478805 A CN1478805 A CN 1478805A CN A031296955 A CNA031296955 A CN A031296955A CN 03129695 A CN03129695 A CN 03129695A CN 1478805 A CN1478805 A CN 1478805A
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Abstract
A process for preparing polybisiloxane containing Si-H bond includes such steps as reduction-coupling reaction of hydrogen-contained hydrocarbyl dichlorosilane and/or dihydrocarbyl dichlorosilane on alkali metal by Wurtz method, alcoholysis, hydrolysis, condensation reaction, and separating. Its advantages are high thermal and optical stability and high machinability.
Description
Technical field: the present invention relates to a kind of organosilicon polymer, particularly a kind of polydisiloxane that comprises si-h bond and preparation method thereof.
Background technology: polydisiloxane has the potential application prospect, as has properties such as heat-resistant stability, electronics performance and photonics performance.Be otherwise known as sily oxide polymkeric substance [Poly (oxydisilanes)] or simply be referred to as poly-sila ether [Poly (silaethers)] of polydisiloxane.Owing to both contained the Si-O-Si key in the main chain of this base polymer, contain the Si-Si bond structure again, thereby this base polymer has good visco-elasticity, the high-low temperature resistant character of polysiloxane concurrently, and some special propertys of polysilane, such as: have intensive uv-absorbing, photoluminescence, electroluminescent and high-conductivity etc.
People such as J.Chojnowski are successively in [J.Chojnowski in 1979; L.Wilkzek.Makromol.Chem., 1979,180:117] and [L.Wilkzek in 1986; S.Rubinsztajn; J.Chojnowski.Makromol.Chem., 1986,187:39] reported and utilized 2,2,3,3,4,4,5,5,6,6-prestox-1,4-dioxy-2,3,5,6-four silicon hexanaphthenes (are write a Chinese character in simplified form
2D
2) as monomer,, obtained full methyl polydisiloxane by cationic ring-opening polymerization.The above-mentioned monomer of relevant afterwards employing carries out ring-opening polymerization, and the research work such as transformation, thermostability mutually that prepare synthetic method, kinetics of polymerization reaction and the full methyl polydisiloxane of full methyl polydisiloxane have obtained certain concern.
As Poland Patent [Chojnowski, Julian; Scibiorek, Marek; Rubinsztajn, Slawomir; Kurjata, Jan.Manufacture of polyoxydisilylene rubbers.Pol.PL 155375 (1992,2)] described and adopted 2,2,3,3,4,4,5,5,6,6-prestox-1,4-dioxy-2,3,5,6-four silicon hexanaphthenes (are write a Chinese character in simplified form
2D
2) under the strong lewis acid katalysis, carry out ring-opening polymerization, prepare the method for full methyl polydisiloxane, this polymkeric substance also can be used to prepare heat-resisting silicon rubber.
In relating to total hydrocarbon base polydisiloxane and effective preparation method thereof, mainly contain following report: Japanese Patent [Kokuni, Nobuki in addition; Nakagawa, Tasuji; Yoshida, Keisuke.Preparation oforganosiloxane-polysilanes.JP 05271419 (1993.10)] described by tetraalkyl dihalo sily oxide and basic metal and in THF, reacted, obtained the preparation method of total hydrocarbon base polydisiloxane with the methyl alcohol alcoholysis; Japanese Patent [Iwasa, Shigeyuki; Nakano, Kaichiro; Maeda, Katsumi; Hasegawa, Etsuo.Silicon-containing sulfonium salts and photoresistcompositions.JP 06342209 (1994.12)] the photoresist material synthetics that contains sulfonium salt and many silicon of oxa-chain link described.
Yet, because the efficient synthesis of this base polymer itself is exactly a problem, above in the described existing research work, all be only to have reported full methyl polydisiloxane, and the stability of the synthetic method of full methyl polydisiloxane, polymerization mechanism, polymkeric substance etc.
Because the full methyl polydisiloxane of above-mentioned report has such as being insoluble to organic solvent, and is poor with the consistency of other compound, is difficult to carry out shortcomings such as chemical modification.Therefore, obtain to can be good at carrying out chemically crosslinked and/or chemical modification, and the polymer materials of can fine performance general relevant with polydisiloxane various performances is very important.
Summary of the invention: polymer architecture characteristics of the present invention have overcome all deficiencies of above-mentioned total hydrocarbon base polydisiloxane, provide a kind of thermal stability preferably, the polydisiloxane that comprises si-h bond with good reactivity.
But the polydisiloxane that comprises si-h bond of the present invention is crosslinkable and/or chemical modification and can not influence the general useful performance relevant with polydisiloxane, as the polydisiloxane that comprises si-h bond of high-low temperature resistant characteristic, better chemical stability, photonics performance, electronics performance etc.; And can be chemically bonded to the polymkeric substance on the various base materials.
The polydisiloxane that comprises si-h bond of the present invention has following structural formula:
Wherein n is the integer of 2-3000 in (1), (2) structural formula, and n and m are the positive integers greater than zero in (3), (4) structural formula, n and m's and be the integer of 2-3000; End group R
1Representing groups such as hydrogen, methyl, ethyl, can be aforementioned group identical or inequality.R
2, R
3, R
4, R
5, R
6Represent alkyl, aryl or heterocyclic group identical or inequality, more commonly used is methyl, ethyl, phenyl group.
The polydisiloxane that comprises si-h bond of the present invention in the following order, step is prepared: (1) alkali-metal dispersion: at N
2Under the gas shiled; with a certain amount of basic metal join fill basic metal own wt 8-10 doubly organic solvent and installed agitator additional, had in the reactor of reflux condensate device, constant pressure funnel of moisture eliminator; be heated to 80-100 ℃ and make alkali metal fusion, high-speed stirring is dispersed into trickle particle with basic metal in organic solvent.(2) dichlorosilane monomer and alkali-metal Wurtz method reductive coupling reaction: by monomer and basic metal reaction mol ratio is 1: 1, and the weight ratio of control organic solvent and total reactant is 8-14 times, stirring, backflow, N
2Protection down, by constant pressure funnel, dichlorosilane monomer and ORGANIC SOLVENT MIXTURES were added drop-wise in 10-30 minute in the above-mentioned scattered alkali-metal system, wherein organic solvent and monomeric weight ratio are 2-4 times, after dropwising, insulation reaction 24-36 hour; (3) hydrolysis, the condensation reaction of Wurtz method reductive coupling reaction product: after above-mentioned dichlorosilane monomer and alkali-metal Wurtz method reductive coupling reaction finish, its reaction solution is reduced to below the room temperature (＜30 ℃), stir afterwards down, splash into proper amount of deionized water by constant pressure funnel.The hydrogen chloride gas that monomeric hydrolytically reactive discharges is as far as possible by blasting N
2Gas is discharged, and continues at room temperature stirring reaction 2-6 hour.
After reaction solution after also can be directly above-mentioned dichlorosilane monomer and basic metal reaction being finished is reduced to room temperature (＜30 ℃), carry out alcoholysis reaction earlier, be hydrolyzed again or partial hydrolysis, condensation reaction.The alcoholysis reaction of reaction solution is carried out below 30 ℃ in control reaction temperature, Yi Bian feed N
2Gas is discharged the hydrogenchloride that reaction generates, Yi Bian continued stirring reaction 2-4 hour; Afterwards control reaction temperature below 30 ℃, stir under, splash into deionized water by constant pressure funnel, carry out whole hydrolysis or partial hydrolysis reaction, continue to blast N
2Gas, stirring reaction 2-6 hour.(4) separation of polymkeric substance: above-mentioned reacting liquid filtering is removed byproduct of reaction alkali metal chloride salt, filtrate adopts deionized water wash to neutral, after the aqueous phase discarded,, remove organic solvent by distillation then and obtain polymkeric substance with anhydrous sodium sulphate or anhydrous magnesium sulfate thorough drying organic phase.Or the exsiccant polymer organic has further heated down at 80-120 ℃ mutually, so that the further condensation reaction 2-6 of hydroxy-end capped polymerization hour, and distillation removal organic solvent obtains high molecular weight polymers.
Dichlorosilane monomer used in the present invention has following structure:
R
1SiHCl
2 (5)
R
1R
2SiCl
2(6) R wherein
1, R
2Represent available various alkyl, aryl or heterocyclic group, wherein R in (6) formula monomer
1, R
2It can be above-mentioned group identical or inequality.
Above-mentioned preparation comprises in the polydisiloxane process of si-h bond, described dichlorosilane monomer can be meet that above-mentioned (5), (6) structural formula require, satisfy a kind of dichlorosilane monomer or two kind and the two or more dichlorosilane mix monomer of following (1)-(4) in describing:
(1) a kind of hydrogeneous dichlorosilane monomer;
(2) two kinds and the monomeric mix monomer of two or more hydrogeneous dichlorosilanes;
(3) a kind of hydrogeneous dichlorosilane monomer and the monomeric mix monomer of a kind of dialkyl dichlorosilane;
(4) two kinds and two or more hydrogeneous dichlorosilane monomer and two kinds and the monomeric mix monomer of two or more dialkyl dichlorosilanes.
Above-mentioned preparation comprises in the polydisiloxane process of si-h bond, the technology of described dichlorosilane monomer and basic metal reaction, can be during aforesaid (1)-(a 4) monomer is described any monomer directly and basic metal react; Also can be two and two above monomers during aforesaid (1)-(4) monomer is described, react with basic metal respectively, after question response is finished respectively again blend carry out subsequent reactions.
Above-mentioned preparation comprises in the polydisiloxane process of si-h bond, and described and basic metal monomer reaction comprises K, Na, Li, and that often use is K, Na.
Above-mentioned preparation comprises in the polydisiloxane process of si-h bond, described organic solvent is the aromatic hydrocarbon of the alkane of 1-8 carbon atom and derivative thereof, a 6-8 carbon atom and derivative thereof etc., that more commonly used is methylene dichloride, trichloromethane, tetrahydrofuran (THF), dioxane, N, dinethylformamide, benzene, monochloro-benzene, toluene, dimethylbenzene equal solvent.
Above-mentioned preparation comprises in the polydisiloxane process of si-h bond, and the usage quantity of described organic solvent is generally 1-20 times of reactant gross weight, and consumption is 4-15 times preferably, and better consumption is 8-12 times.Wherein major part is scattered in wherein basic metal, to form basic metal fine particles (basic metal sand); 1-4 amount is doubly mixed with monomer, to reduce monomeric volatility; Being more preferably 2-4 amount doubly mixes with monomer.
Above-mentioned preparation comprises in the polydisiloxane process of si-h bond, and the absolute alcohol that described alcoholysis reaction is used is methyl alcohol, ethanol or Virahol etc.
Above-mentioned preparation comprises in the polydisiloxane process of si-h bond, the 1-8 that the amount of the used deionized water of described hydrolysis reaction is generally monomer dichlorosilane molar weight doubly, preferably consumption be monomer dichlorosilane molar weight 2-6 doubly.
Above-mentioned preparation comprises in the polydisiloxane process of si-h bond, filtering and removing inorganic salt branch hydrolysate afterwards still is aqueous strongly-acid organic solution, wherein the removal of strong acid hydrogenchloride can adopt sig water slowly to neutralize, also the mode that can adopt deionized water to wash.If using the sig water employed sig water that slowly neutralizes can be mineral alkali as Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3Etc. dilute solution; Also can be organic amine alkali as dilute solutions such as Trimethylamine 99, triethylamines.But from the angle of protection si-h bond, the method for removing strong acid hydrogenchloride more effectively, safely be adopt go dried up, in a small amount of mode repeatedly with its washing to neutral.
Above-mentioned preparation comprises in the polydisiloxane process of si-h bond, described washed to neutral product organic solution through separate removing moisture, after adopting thorough dryings such as anhydrous sodium sulphate or anhydrous magnesium sulfate, the general employing standard isolation technique of removing of organic solvent is handled, can air distillation or the method for underpressure distillation directly remove organic solvent and obtain polymer product of the present invention.
The polydisiloxane that comprises si-h bond of the present invention dissolves in following organic solvent tetrahydrofuran, dioxane, chloroform, N, dinethylformamide etc.
The polydisiloxane that comprises si-h bond of the present invention can be uncrosslinked or crosslinked.
The polydisiloxane that comprises si-h bond of the present invention can with the organoalkoxysilane coupling agent more than two senses, or carry out cross-linking vulcanized reaction with reactive polysiloxane.In addition, the polydisiloxane that comprises si-h bond of the present invention can also comprise at least a silane, siloxanes, polysiloxane or their combination.Silane, siloxanes, polysiloxane can be by to its modification, also can being by reacting to its modification with the polydisiloxane that comprises si-h bond with the polydisiloxane blend that comprises si-h bond.The material of any siliceous hydroxy functional group all can react with the polydisiloxane that comprises si-h bond of the present invention.
The polydisiloxane of si-h bond that comprises of the present invention is in various Application for Field, described application comprises, but not only is confined to comprise the cross-linked polymer of the sily oxide of si-h bond, the polydisiloxane elasticoplastic body that comprises si-h bond, functional paint, ceramic forerunner, electronics material, photonics material etc.The polydisiloxane that comprises si-h bond of the present invention also can be used as membrane component and other application.
Existing studies show that of the polydisiloxane that comprises si-h bond of the present invention's preparation, this polymkeric substance has the intensive uv-absorbing, unique photoluminescence performance, good workability, thermostability and light stability, and can be crosslinked or further react subsequently.
In addition, the unique texture that comprises the polydisiloxane of si-h bond of the present invention, given the response capacity of this base polymer, can further improve chemical adhesion, as the binding property of improvement with inorganic substrate such as glass, metal, metal oxide and other base materials to base material.And the polydisiloxane that comprises si-h bond of the present invention can be used as modified silicon rubber, can form the IPN alloy between polydisiloxane that comprises si-h bond and silicon rubber.
The polydisiloxane that comprises si-h bond of the present invention can be used as a component in the polymer blend, can add any compatible polymers and form blend, thereby corresponding other polymer materials is carried out modification.
Description of drawings: figure-1 comprises the infrared spectra of the polydisiloxane of si-h bond for embodiment 1 target product;
Figure-2 comprises the infrared spectra of the polydisiloxane of si-h bond for embodiment 3 target products;
Figure-3 comprises the proton magnetic spectrum of the polydisiloxane of si-h bond for embodiment 1 target product;
Figure-4 comprises the proton magnetic spectrum of the polydisiloxane of si-h bond for embodiment 3 target products;
Figure-5 comprises the GPC molecule of the polydisiloxane of si-h bond for embodiment 1 target product
The flow measurement curve.
Specific implementation method: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
(1) 2.95 gram sodium Metal 99.5s are put into fill the 150mL solvent toluene, sealed stirrer, thermometer, N be housed
2Gas shiled, install additional in the reactor of reflux condensing tube of drying tube, at 105 ℃, N
2Under protection, the high-speed stirring, sodium Metal 99.5 is separated into fine particle.
(2) with the mixture of 14.72 gram methyl hydrogen dichlorosilane and 20mL toluene, under quick stirring, black out condition, be added drop-wise to fast in the above-mentioned toluene solvant that disperses sodium Metal 99.5 by constant pressure funnel, temperature control 100-105 ℃ is continued reaction 12 hours afterwards.
(3) treat that monomer and sodium Metal 99.5 react completely after, reaction solution is cooled to room temperature (below 30 ℃), and control reaction temperature is below 30 ℃, stir the deionized waters that drip 7.0 grams down at a slow speed.Continue to blast N
2The hydrogenchloride that gas eliminating hydrolysis reaction generates 2 hours, and will react the hydrogen chloride gas body and function alkali lye absorption that discharges.
(4) with after the salt settling that generates in the hydrolysis reaction product, the suction filtration reaction product is with separating by-products sodium-chlor.Filtrate is transferred in the separating funnel, discarded lower floor's water.Toluene solution with the deionized water wash product is extremely neutral, and the amount of each deionized water that uses is advisable with 15-20mL during washing.Remove moisture after leaving standstill, put into the anhydrous sodium sulphate of 3.0 grams in the toluene solution of product, standing over night obtains light yellow transparent solution.Adopt air distillation to remove solvent toluene, when the mother liquor temperature rises to 200 ℃, stop distillation, obtain the faint yellow transparent thickness product of 5.66 grams.Productive rate is 85%.IR (film, cm by the KBr wafer
-1): SiSi stretching vibration 413cm
-1, SiOSi stretching vibration 1000-1100,750-850cm
-1, SiH stretching vibration (splitting branch) 2168,2084cm
-1, SiCH
3Formation vibration 700-800,1264,1407cm
-1, CH
3Stretching vibration 2796,2893,2963cm
-1 1HNMR (CDCl
3, δ, ppm): 5.27 (Si-OH), 4.72,4.67 (Si-H), 0.21 (Si-CH
3); Recording number-average molecular weight is 24,889, and weight-average molecular weight is 34,328, and distribution coefficient is 1.38.
Embodiment 2:
(1) 1.82 gram sodium Metal 99.5s are put into fill the 60mL solvent toluene, sealed stirrer, thermometer, N2 gas shiled be housed, install the reactor of the reflux condensing tube of drying tube additional; under 105 ℃, N2 protection, high-speed stirring, sodium Metal 99.5 is separated into fine particle.
(2) with the mixture of 9.10 gram methyl hydrogen dichlorosilane and 10mL toluene, under quick stirring, black out condition, be added drop-wise to fast in the above-mentioned toluene solvant that disperses sodium Metal 99.5 by constant pressure funnel, temperature control 100-105 ℃ is continued reaction 12 hours afterwards.
With above-mentioned same operation, with the 1.85 gram sodium Metal 99.5s of having removed oxide compound put into another fill the 60mL solvent toluene, sealed stirrer, thermometer, N be housed
2Gas shiled, install additional in the reactor of reflux condensing tube of drying tube, at 105 ℃, N
2Under protection, the high-speed stirring; sodium Metal 99.5 is separated into fine particle; mixture with 10.37 gram dimethyldichlorosilane(DMCS)s and 20mL toluene; under quick stirring, black out condition; be added drop-wise to fast in the above-mentioned toluene solvant that disperses sodium Metal 99.5 by constant pressure funnel, temperature control 100-105 ℃ is continued reaction 12 hours afterwards.
(3) treat that monomer in above-mentioned two reactors and sodium Metal 99.5 react completely respectively after, reaction solution is cooled to room temperature (below 30 ℃), reaction product in two reactors is transferred in the same reactor, and control reaction temperature stirs the deionized water that drips 9.0 grams down at a slow speed below 30 ℃.Continue to blast N
2The hydrogenchloride that gas eliminating hydrolysis reaction generates 2 hours, and will react the hydrogen chloride gas body and function alkali lye absorption that discharges.
(4) with after the salt settling that generates in the hydrolysis reaction product, the suction filtration reaction product is with separating by-products sodium-chlor.Filtrate is transferred in the separating funnel, discarded lower floor's water.Toluene solution with the deionized water wash product is extremely neutral, and the amount of each deionized water that uses is advisable with 15-20mL during washing.Remove moisture after leaving standstill, in the toluene solution of product, put into the anhydrous sodium sulphate of 3.5 grams, standing over night.Obtain light yellow transparent solution.Adopt rotatory evaporator, under 45-50 ℃, distillation removes solvent toluene, obtains the faint yellow transparent thickness product of 7.84 grams.Productive rate is 83%.IR (film, cm by the KBr wafer
-1): SiSi stretching vibration 413cm
-1, SiOSi stretching vibration 1000-1100,750-850cm
-1, branch 2168,2084cm are split in the SiH stretching vibration
-1, SiCH
3Formation vibration 700-800,1264,1407cm
-1, CH
3Stretching vibration 2796,2893,2963cm
-1,
1HNMR (CDCl
3, δ, ppm): 5.27 (Si-OH), 4.71,4.69 (Si-H), 0.19 (SiHCH
3), 0.08 (Si (CH
3)
2).
Embodiment 3:
(1) 3.10 gram potassium metals are put into fill the 100mL solvent toluene, sealed stirrer, thermometer, N2 gas shiled be housed, install the reactor of the reflux condensing tube of drying tube additional; under 80 ℃, N2 protection, high-speed stirring, sodium Metal 99.5 is separated into fine particle.
(2) restrain the mixture that methyl hydrogen dichlorosilane, 5.03 restrain dimethyldichlorosilane(DMCS)s and 20mL toluene with 4.48, under quick stirring, black out condition, be added drop-wise to fast in the above-mentioned toluene solvant that disperses potassium metal by constant pressure funnel, temperature control 80-85 ℃ is continued reaction 12 hours afterwards.
(3) treat that monomer and potassium metal react completely after, reaction solution is cooled to room temperature (below 30 ℃), and control reaction temperature is below 30 ℃, stir down the deionized water of Dropwise 5 .0 gram at a slow speed.Continue to blast N2 gas and get rid of the hydrogenchloride 2 hours that hydrolysis reaction generates, and will react the hydrogen chloride gas body and function alkali lye absorption that discharges.
(4) with after the salt settling that generates in the hydrolysis reaction product, the suction filtration reaction product is with the separating by-products chlorination. potassium.Filtrate is transferred in the separating funnel, discarded lower floor's water.Toluene solution with the deionized water wash product is extremely neutral, and the amount of each deionized water that uses is advisable with 15-20mL during washing.Remove moisture after leaving standstill, in the toluene solution of product, put into the anhydrous sodium sulphate of 2.5 grams, standing over night.Obtain light yellow transparent solution.Adopt air distillation to remove solvent toluene, when the mother liquor temperature rises to 200 ℃, stop distillation, obtain the faint yellow transparent thickness product of 3.9 grams.Productive rate is 83%.IR (film, cm by the KBr wafer
-1): SiSi stretching vibration 413cm
-1, SiOSi stretching vibration 1000-1100,750-850cm
-1, branch 2168,2084cm are split in the SiH stretching vibration
-1, SiCH
3Formation vibration 700-800,1264,1407cm
-1, CH
3Stretching vibration 2796,2893,2963cm
-1 1HNMR (CDCl
3, δ, ppm): 5.27 (Si-OH), 4.71,4.69 (Si-H), 0.18 (SiHCH
3), 0.09 (Si (CH
3)
2).
Claims (6)
1. a polydisiloxane that comprises si-h bond is characterized in that this main polymer chain contains silicon silica repeating segment, side chain contains si-h bond and silicon hydrocarbyl group, its structure such as following (1)-(4) formula:
Wherein n is the integer of 2-3000 in (1), (2) structural formula; (3), n and m are the positive integers greater than zero in (4) structural formula, n and m's and be the integer of 2-3000; End group R
1Representing H, methyl, ethyl, sec.-propyl, can be aforementioned group identical or inequality; R
2, R
3, R
4, R
5, R
6Represent methyl, ethyl, phenyl identical or inequality.
2. preparation method who comprises the polydisiloxane of si-h bond is characterized in that step is carried out in the following order:
(1) alkali-metal dispersion: at N
2Under the gas shiled, a certain amount of metal K or Na and their weight 8-10 organic solvent have doubly been installed additional agitator, had in the reactor of reflux condensate device, constant pressure funnel of moisture eliminator, be heated to 80-100 ℃ and make metal K or Na fusion, and under high-speed stirring, metal K or Na are dispersed into trickle particle in organic solvent;
(2) dichlorosilane monomer and alkali-metal Wurtz method reductive coupling reaction: by monomer and basic metal reaction mol ratio is 1: 1, and the weight ratio of control organic solvent and total reactant is 8-14 times, stirring, backflow, N
2Protection down, by constant pressure funnel, dichlorosilane monomer and ORGANIC SOLVENT MIXTURES were added drop-wise in 15-20 minute in the system of above-mentioned scattered metal K or Na, wherein organic solvent and monomeric weight ratio are 2-4 times, after dropwising, insulation reaction 24-36 hour;
(3) hydrolysis, the condensation reaction of Wurtz method reductive coupling reaction product: after above-mentioned dichlorosilane monomer and alkali-metal Wurtz method reductive coupling reaction finish, reaction solution is reduced to below the room temperature (＜30 ℃), afterwards under this temperature, splash into monomer molar amount 1-8 deionized water doubly by constant pressure funnel and mix reaction, the hydrogen chloride gas that monomeric hydrolytically reactive discharges is as far as possible by blasting N
2Gas is got rid of, and continues at room temperature stirring reaction 2-6 hour;
After reaction solution after also can be directly above-mentioned dichlorosilane monomer and basic metal reaction being finished is reduced to room temperature (＜30 ℃), carry out alcoholysis reaction earlier, be hydrolyzed again or partial hydrolysis, condensation reaction, the alcoholysis reaction of reaction solution is in control reaction temperature below 30 ℃, at one hour with the interior monomer molar amount 2-4 alcohol doubly that in above-mentioned reaction solution, splashes into, Yi Bian feed N
2Discharge the hydrogenchloride that reaction generates, continued stirring reaction 2-4 hour on one side, control reaction temperature splashes into monomer molar amount 0.1-8 deionized water doubly below 30 ℃, under the stirring by constant pressure funnel afterwards, carry out whole hydrolysis or partial hydrolysis reaction, continue to blast N
2Gas, stirring reaction 2-6 hour;
(4) separation of polymkeric substance: above-mentioned reacting liquid filtering is removed byproduct of reaction alkali metal chloride salt, filtrate discards acidic aqueous solution, and it is extremely neutral with deionized water wash, after the aqueous phase discarded, with an amount of anhydrous sodium sulphate or anhydrous magnesium sulfate drying organic phase, and remove organic solvent by distillation and obtain polydisiloxane; Or the above-mentioned polymer organic of exsiccant has further heated down at 80-120 ℃ mutually, so that the further condensation reaction 2-6 of hydroxy-end capped polymerization hour, and distillation removal organic solvent obtains the high-molecular weight polydisiloxane.
3. a kind of preparation method who comprises the polydisiloxane of si-h bond according to claim 2 is characterized in that described dichlorosilane monomer has the following structures formula:
R
1SiHCl
2 (5)
R
1R
2SiCl
2 (6)
R wherein
1, R
2Represent methylidene, ethyl, phenyl, wherein R in (6) formula monomer
1, R
2It can be above-mentioned group identical or inequality; And be to meet following (1)-(4) a kind of dichlorosilane monomer in describing or the combination of two kinds and two or more dichlorosilane mix monomers:
(1) a kind of hydrogeneous dichlorosilane monomer;
(2) two kinds and the monomeric mix monomer of two or more hydrogeneous dichlorosilanes;
(3) a kind of hydrogeneous dichlorosilane monomer and the monomeric mix monomer of a kind of dialkyl dichlorosilane;
(4) two kinds and two or more hydrogeneous dichlorosilane monomer and two kinds and the monomeric mix monomer of two or more dialkyl dichlorosilanes.
4. a kind of preparation method who comprises the polydisiloxane of si-h bond according to claim 2, the technology that it is characterized in that described dichlorosilane monomer and metal K or Na reaction, can be any monomer during (1) as claimed in claim 4-(4) monomer is described, directly and metal K or Na react; Also can be two and two above monomers during (1) as claimed in claim 4-(4) monomer is described, react with metal K or Na respectively, after reaction is finished respectively again blend carry out subsequent reactions.
5. a kind of preparation method who comprises the polydisiloxane of si-h bond according to claim 2, it is characterized in that described organic solvent comprises: methylene dichloride, trichloromethane, tetrahydrofuran (THF), dioxane, N, dinethylformamide, benzene, monochloro-benzene, toluene, xylene solvent.
6. a kind of preparation method who comprises the polydisiloxane of si-h bond according to claim 2 is characterized in that the alcohol that described alcoholysis reaction is used comprises: methyl alcohol, ethanol and Virahol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191019B (en) * | 2006-11-29 | 2011-05-04 | 烟台大学 | Addition type cross-linking vulcanized polydisiloxane elastomer |
| CN101605838B (en) * | 2006-10-03 | 2013-09-25 | 国家科研中心 | Method for treating surfaces containing Si-H groups |
-
2003
- 2003-07-03 CN CNA031296955A patent/CN1478805A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101605838B (en) * | 2006-10-03 | 2013-09-25 | 国家科研中心 | Method for treating surfaces containing Si-H groups |
| CN101191019B (en) * | 2006-11-29 | 2011-05-04 | 烟台大学 | Addition type cross-linking vulcanized polydisiloxane elastomer |
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