CN102641748A - Preparation method of hydroxyl burning-rate catalyst for substituent ferrocenylsilanes grafting and product thereof - Google Patents
Preparation method of hydroxyl burning-rate catalyst for substituent ferrocenylsilanes grafting and product thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a hydroxyl burning-rate catalyst for substituent ferrocenylsilanes grafting and a product thereof. The preparation method is characterized by including the specific steps of firstly, performing chloroalkyl modification to substituent ferrocene with chloroalkyl ether by utilizing zinc chloride as a catalyst to obtain substituent chloroalkyl ferrocene at one step; secondly, leading the substituent chloroalkyl ferrocene to react with magnesium chips under effect of iodine initiation, and preparing substituent ferrocenylsilanes by adding silanization reagent in a refluxing manner after reaction; thirdly, preparing hydroxyl-terminated polybutadiene for substituent ferrocenylsilanes grafting, namely the hydroxyl burning-rate catalyst for substituent ferrocenylsilanes grafting by means of hydrosilylation between the substituent ferrocenylsilanes and the hydroxyl-terminated polybutadiene under action of transition metallic catalysts. The preparation method is simple, low in cost of materials and risks. The hydroxyl burning-rate catalyst prepared by the preparation method is low in mobility rate, high in iron content and capable of improving burning rate of propellants effectively when applied to the same.
Description
Technical field
The present invention relates to a kind of efficient burningrate catalyst of propellant that is used for aerospace industry, particularly a kind of preparation method who replaces ferrocene silane grafting fourth hydroxyl burningrate catalyst and products thereof.
Background technology
In solid propellant, adding efficient burningrate catalyst, is one of optimal path that improves propellant burning rate.The ferrocene analog derivative has very high combustion speed catalytic efficiency, has been widely used in the solid propellant field, in aerospace industry, has brought into play enormous function.
Even so, but up to the present, the burningrate catalyst of being developed all has its weak point.The major defect of alkylferrocenes is that molecular weight is little, and volatility is big, has serious animal migration.Kato hot [two (ethyl dicyclopentadienyl iron) propane] is that a kind of molecular weight is big, and iron content is high, the burningrate catalyst that mechanical property is excellent, but still show tangible animal migration after the long-time placement of propellant.Migration for fear of catalyst; The report of the ferrocene derivatives that contains hydroxyl, amido, sulfydryl isoreactivity group has appearred utilizing; Active group wherein can with the curing agent isocyanates effect of fourth hydroxyl propellant; Crosslinked in macromolecule network, but the introducing of this compounds must add excessive curing agent, causes the reduction greatly of mechanical properties of propellant.
Ferrocene silane can with the two key generation silicon hydrogenations on the fourth hydroxyl glue macromolecular chain, be grafted on the macromolecular chain ferrocene is silica-based, thereby effectively avoided problems such as the ubiquitous migration of other ferrocene-containing compounds, mechanical property.The quality quality of ferrocene silane directly has influence on the combustion speed catalytic performance of graft product.The method of existing synthetic ferrocene silane mainly is through Friedel-Crafts reaction and the synthetic ferrocene acyl chlorides of ferrocene reaction; And then with the synthetic chloro alkylferrocenes of metal hydride reduction; Then synthesize organo-lithium compound with lithium metal, thus last and dimethylchlorosilane reaction preparation ferrocene silane.Not only process is complicated, process conditions are harsh, operation easier is big, and yield is low, and is dangerous big.
Summary of the invention
The invention provides preparation method of a kind of fourth hydroxyl burningrate catalyst that replaces the grafting of ferrocene silane and products thereof; It specifically is to carry out the chlorine alkylation modification through the chlorine alkyl ether to replacing ferrocene; Single step reaction obtains the chlorine alkylation and replaces ferrocene; Then replacement ferrocene RMgBr and the silylating reagent prepared in reaction through preparation replaces ferrocene silane, and last and end hydroxy butadiene generation silicon hydrogenation prepares the fourth hydroxyl burningrate catalyst that replaces the grafting of ferrocene silane.Its technical process is simple; Cost of material is low, and is dangerous little, when the fourth hydroxyl burningrate catalyst of the replacement ferrocene silane grafting of preparation uses in being applied to propellant; Mobility is little; Not only solved and added the migration problem that the solid propellant combustion rate catalyst exists, and iron-holder is high, can effectively improve the combustion speed of propellant.
For solving the technical problem that the present invention proposes, the technical scheme that the present invention adopted is:
A kind of preparation method who replaces the fourth hydroxyl burningrate catalyst of ferrocene silane grafting, it is characterized in that: it comprises following concrete steps:
(1) with the zinc chloride be catalyst, carry out the chlorine alkylation modification with the chlorine alkyl ether to replacing ferrocene, single step reaction obtains the chlorine alkylation and replaces ferrocene; (2) under the effect that iodine causes, above-mentioned chlorine alkylation replacement ferrocene and magnesium chips are reacted, add silylating reagent backflow preparation after reaction finishes and replace ferrocene silane;
(3) under the effect of transition-metal catalyst, replace the silicon hydrogenation of ferrocene silane and end hydroxy butadiene, the end hydroxy butadiene of preparation replacement ferrocene silane grafting promptly replaces the fourth hydroxyl burningrate catalyst of ferrocene silane grafting.
Press such scheme, described replacement ferrocene is: the mixing of one or more in bromo ferrocene, iodo ferrocene, ferrocenecarboxylic acid, ferrocene amine, methyl ferrocene, ethyl dicyclopentadienyl iron, the propyl group ferrocene.
Press such scheme, described chlorine alkyl ether is: chloromethyl methyl ether, 2-chloroethyl methyl ether, 3-chloropropyl methyl ether, 4-chlorobutyl methyl ether, 1, the mixing of one or more in the 4-dichloro methyl butyl ether.
Press such scheme; The concrete steps of said step (1) are: in amount of substance; Replacing ferrocene with 1 part is dissolved in the solvent; Add 0.1-2 part chlorine alkyl ether, 0.01-0.1 part zinc chloride again, back flow reaction 2-24 hour, reaction finishes after washing, separatory, drying, revolve to steam and obtain the chlorine alkylation and replace ferrocene.
Press such scheme, described silylating reagent is a chlorodimethyl silane.
Press such scheme, the concrete steps of said step (2) are: in amount of substance, in the airtight reaction vessel that is full of nitrogen of drying, add dry solvent, 0.5-2 part magnesium chips; Add the alkylation of 0.1-0.5 part chlorine then and replace ferrocene, a little iodine crystalline substance; The low-grade fever initiation reaction, and then drip remaining chlorine alkylation replacement ferrocene, the total amount that the chlorine alkylation of twice dropping replaces ferrocene is 1 part; Back flow reaction 2-24 hour; The silylating reagent that then adds 0.5-2 part back flow reaction 2-24 hour, washing, separatory, revolves to steam and obtains replacing ferrocene silane.
Press such scheme, the transition-metal catalyst in the said step (3) is one or more the mixing in chloroplatinic acid, the triphenylphosphine radium chloride.
Press such scheme, described end hydroxy butadiene molecular weight is 1000-8000.
Press such scheme; The concrete steps of said step (3) are: in amount of substance; In the reaction vessel of drying, add dry solvent; Add 0.001-0.01 part catalyst, drip the solution that contains 1 part of ferrocene silane and 0.01-0.1 part end hydroxy butadiene, dropwise the back can obtain the grafting of ferrocene silane after back flow reaction 2-24 hour in 30-110 ℃ of scope fourth hydroxyl burningrate catalyst.
Press such scheme, the solvent in said step (1) or step (2) or the step (3) is one or more the mixing in carrene, chloroform, oxolane, dimethyl formamide, dimethylacetylamide, methyl-sulfoxide, the toluene.
The fourth hydroxyl burningrate catalyst of the replacement ferrocene silane grafting that obtains according to above-mentioned preparation method.
Basic principle of the present invention is:
(1) with the zinc chloride be catalyst, carry out the chlorine alkylation modification with the chlorine alkyl ether to replacing ferrocene, single step reaction obtains the chlorine alkylation and replaces ferrocene;
(2) under the effect that iodine causes, above-mentioned chlorine alkylation replacement ferrocene and magnesium chips are reacted preparation ferrocene Ge Shi
Reagent, reaction finish back adding silylating reagent backflow preparation and replace ferrocene silane;
(3) under the effect of transition-metal catalyst; The end hydroxy butadiene that the silicon hydrogenation that replaces ferrocene silane and end hydroxy butadiene, preparation replace the grafting of ferrocene silane promptly replaces fourth hydroxyl burningrate catalyst of ferrocene silane grafting and preparation method thereof.
Beneficial effect of the present invention: (1) is compared with traditional ferrocene chlorine alkylation modification, uses chlorine alkyl oxide modified, and single step reaction obtains the chlorine alkylation and replaces ferrocene, and technical process is simple, feed stock conversion is high; (2) realize the silanization of ferrocene through preparing the ferrocene RMgBr, avoided the use of lithium metal, dangerous low; (3) be liquid under the product normal temperature, be used for composite solidpropellant and can play plasticizer; (4) iron-holder is high, can effectively improve the combustion speed of propellant.
Description of drawings
Fig. 1 is preparation method's process chart of the present invention.
The specific embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with accompanying drawing, embodiment, but content of the present invention not only is confined to following embodiment; Should not be regarded as limitation of the present invention yet.
Embodiment 1:
(1) in the there-necked flask that agitator, condenser and thermometer are housed, adds 26.5g 1'-bromo ferrocene and 100ml dichloromethane solvent, dispersed with stirring under the room temperature, the mixture of adding 0.805g chloromethyl methyl ether and 0.136g zinc chloride.Slowly be warming up to 39 ℃ of back flow reaction 2 hours.Reaction finishes after catalyst, separatory are removed in washing removes water, drying and remove moisture in the organic facies, revolve and steam that removing desolvates obtains 1'-bromine chloromethyl ferrocene.
(2) in the reaction bulb of abundant drying and inflated with nitrogen, add the magnesium chips of 0.6g and the tetrahydrofuran solvent of 50ml drying; Adding 20ml contains the tetrahydrofuran solution of 7.83g 1'-bromine chloromethyl ferrocene; Add a little iodine crystalline substance earlier and carry out initiation reaction, low-grade fever is urged its reaction.Drip the tetrahydrofuran solution that 20ml contains 7.83g 1'-bromine chloromethyl ferrocene again after causing end; 65 ℃ of backflows add the 2.36g dimethylchlorosilane after 2 hours; Continued back flow reaction 2 hours, through washing, separatory, revolve steam (1'-bromine ferrocene methyl) dimethylsilane.
(3) in the reaction vessel of drying; Add 50ml dry toluene, 25.9mg chloroplatinic acid; Drip the toluene solution that contains 13.47g (1'-bromine ferrocene methyl) dimethylsilane and 2.5g end hydroxy butadiene (molecular weight is 5000) in 1 hour, be heated to 110 ℃ of reactions after dropwising and revolved the fourth hydroxyl burningrate catalyst that steaming can obtain (1'-bromine ferrocene methyl) dimethylsilane grafting in 2 hours.
Embodiment 2:
(1) in the there-necked flask that agitator, condenser and thermometer are housed, adds the chloroform of 31.2g1'-iodo ferrocene and 100ml, dispersed with stirring under the room temperature, the mixture of adding 18.9g chloroethyl methyl ether and 1.36g zinc chloride.Slowly be warming up to 61 ℃ of back flow reaction 24 hours.Reaction finishes after washing, separatory, drying, revolve to steam and obtain 1'-iodine chloroethyl ferrocene.
(2) in the reaction bulb of abundant drying and inflated with nitrogen, add the magnesium chips of 1.2g and the oxolane of 50ml drying, add the tetrahydrofuran solution that 20ml contains 1.38g 1'-iodine chloroethyl ferrocene, add the brilliant initiation reaction of a little iodine earlier, low-grade fever is urged its reaction.Cause the tetrahydrofuran solution that drips 12.4g 1'-iodine chloroethyl ferrocene after finishing again; 65 ℃ of back flow reaction add the 6.96g dimethylchlorosilane after 24 hours; Continue to reflux 24 hours, through washing, separatory, revolve steam (1'-iodine ferrocene ethyl) dimethylsilane.
(3) in the reaction vessel of drying; Add 50ml dry dimethyl formamide, 259mg chloroplatinic acid; Drip the dimethyl formamide solution that contains 20g (1'-iodine ferrocene ethyl) dimethylsilane and 5g end hydroxy butadiene (molecular weight is 1000) in 1 hour, dropwise to react under back 100 ℃ and revolved the fourth hydroxyl burningrate catalyst that steaming can obtain (1'-iodine ferrocene ethyl) dimethylsilane grafting in 4 hours.
Embodiment 3:
(1) in the there-necked flask that agitator, condenser and thermometer are housed, add 23g1'-formic acid ferrocene and 10ml tetrahydrofuran solvent, dispersed with stirring under the room temperature adds the mixture of 10.85 chloropropyl methyl ethers and 0.272g zinc chloride.Slowly be warming up to 65 ℃ of back flow reaction 8 hours.Reaction finishes after washing, separatory, drying, revolve to steam and obtain 1'-formic acid chloropropyl ferrocene.
(2) in the reaction bulb of abundant drying and inflated with nitrogen, add the magnesium chips of 0.9g and the dimethylacetylamide of 50ml drying; Adding 20ml contains the dimethyl sulfoxide solution of 3.85g 1'-formic acid chloropropyl ferrocene; Add a little earlier, the brilliant initiation reaction of iodine, low-grade fever is urged its reaction.Drip the dimethyl sulfoxide solution that 20ml contains 8.99g 1'-formic acid chloropropyl ferrocene again after causing end; 100 ℃ of backflows add the 4.56g dimethylchlorosilane after 6 hours; Continue to reflux 20 hours, through washing, separatory, revolve steam (1'-formic acid ferrocene propyl group) dimethylsilane.
(3) in the reaction vessel of drying; Add 50ml dry toluene, 51.8mg chloroplatinic acid; Dropping contains the toluene solution of 15.8g (1'-formic acid ferrocene propyl group) dimethylsilane and 10g end hydroxy butadiene (molecular weight is 2000), drips back 100 ℃ of reactions and revolves the fourth hydroxyl burningrate catalyst that steaming can obtain (1'-formic acid ferrocene propyl group) dimethylsilane grafting in 6 hours.
Embodiment 4:
(1) in the there-necked flask that agitator, condenser and thermometer are housed, adds amino ferrocene of 1 part of 20g1-and tetrahydrofuran solvent, dispersed with stirring under the room temperature, the mixture of adding 12.3g chlorobutyl methyl ether and 0.544g zinc chloride.Back flow reaction 8 hours.Reaction finishes after washing, separatory, drying, revolve to steam and obtain the amino chlorobutyl ferrocene of 1-.
(2) in the reaction bulb of abundant drying and inflated with nitrogen, add the magnesium chips of 0.7g and the oxolane of 50ml drying, add the toluene solution that 20ml contains the amino chlorobutyl ferrocene of 7.29g 1-, add a little earlier, the initiation reaction of iodine crystalline substance, low-grade fever is urged its reaction.Dripping 20ml after cause finishing again and containing the toluene solution of the amino chlorobutyl ferrocene of 7.29g 1-, refluxing adds the 6.84g dimethylchlorosilane after 6 hours, continue to reflux 18 hours, through washing, separatory, revolve steam (1-amino ferrocene butyl) dimethylsilane.
(3) in the reaction vessel of drying; Add 50ml dry methyl-sulfoxide, 46.25mg triphenylphosphine radium chloride; Dropping contains the dimethyl sulfoxide solution of 15.8g (the amino ferrocene butyl of 1-) dimethylsilane and 25g end hydroxy butadiene (molecular weight is 5000), dropwises to react under back 100 ℃ to revolve the fourth hydroxyl burningrate catalyst that steaming can obtain (the amino ferrocene butyl of 1-) dimethylsilane grafting in 10 hours.
Embodiment 5:
(1) in the there-necked flask that agitator, condenser and thermometer are housed, add the toluene solvant of 21.4g 1-methyl ferrocene and 100ml, dispersed with stirring under the room temperature adds 15.7g 1, the mixture of 4-dichloro methyl butyl ether and 0.846g zinc chloride.Slowly be warming up to 110 ℃ of back flow reaction 8 hours.Reaction finishes after washing, separatory, drying, revolve to steam and obtain 1-methyl chloride methyl ferrocene.
(2) in the reaction bulb of abundant drying and inflated with nitrogen, add the magnesium chips of 0.8g and the oxolane of 50ml drying, add the dimethyl formamide solution that contains 6.18g 1-methyl chloride methyl ferrocene, add a little earlier, the brilliant initiation reaction of iodine, low-grade fever is urged its reaction.Drip the dimethyl formamide solution that contains 6.18g 1-methyl chloride methyl ferrocene again after causing end; 65 ℃ of backflows add the 6.84g dimethylchlorosilane after 6 hours; Continue to reflux 18 hours, through washing, separatory, revolve steam (1-methyl ferrocene methyl) dimethylsilane.
(3) in the reaction vessel of drying; Add 50ml dry dimethylacetylamide, 462.5mg triphenylphosphine radium chloride; Dropping contains the dimethylacetamide solution of 15.3g (1-methyl ferrocene methyl) dimethylsilane and 40g end hydroxy butadiene (molecular weight is 8000), dropwises to react under back 60 ℃ to revolve the fourth hydroxyl burningrate catalyst that steaming can obtain (1-methyl ferrocene methyl) dimethylsilane in 18 hours.
Embodiment 6:
(1) in the there-necked flask that agitator, condenser and thermometer are housed, adds 22.8g1-propyl group ferrocene and toluene solvant, dispersed with stirring under the room temperature, the mixture of adding 3.22g chloromethyl methyl ether and 0.272g zinc chloride.Back flow reaction 8 hours.Reaction finishes after washing, separatory, drying, revolve to steam and obtain 1-propyl chloride methyl ferrocene.
(2) in the reaction bulb of abundant drying and inflated with nitrogen, add the magnesium chips of 0.9g and the oxolane of 50ml drying, add the dimethyl formamide solution that contains 3.46g 1-propyl chloride methyl ferrocene, add a little earlier, the brilliant initiation reaction of iodine, low-grade fever is urged its reaction.Drip the dimethyl formamide solution of 10.37g 1-propyl chloride methyl ferrocene after cause finishing again, refluxing adds the 9.46g dimethylchlorosilane after 6 hours, continue backflow 18 hours, through washing, separatory, revolve steam (1-propyl chloride methyl) dimethylsilane.
(3) in the reaction vessel of drying; Add 50ml dry dimethylacetylamide, 92.5mg triphenylphosphine radium chloride; Dropping contains the dimethylacetamide solution of 16.78g (1-propyl chloride methyl) dimethylsilane and 20g end hydroxy butadiene (molecular weight is 3000), dropwises to react under back 80 ℃ to revolve the fourth hydroxyl burningrate catalyst that steaming can obtain (1-propyl chloride methyl) dimethylsilane in 10 hours.
Main performance index of the present invention and assay method:
The outward appearance of embodiment 1-6 product: it is the brownish red oily liquids that the chlorine alkylation that step (1) prepares replaces ferrocene; The replacement ferrocene silane that step (2) prepares is orange red oily liquids; The end hydroxy butadiene of the replacement ferrocene silane grafting that step (3) prepares is orange-yellow thick liquid.
The fourth hydroxyl Preparation of Catalyst of the replacement ferrocene silane grafting of embodiment 1-6 preparation is become propellant, carry out catalytic efficiency, animal migration, and the experiment of propellant processing performance.Concrete experimentation is:
The propellant preparation: adopt the high combustion speed of end hydroxy butadiene/ammonium perchlorate/aluminium (HTPB/AP/Al) prescription, wherein the Al mass fraction is 15%, and the AP mass fraction is 67%, and all the other are bonding system and various auxiliary agent.The principle suitable according to iron content, blank formula counts the consumption of burningrate catalyst in bonding system or the auxiliary agent.Add each component of propellant in 5L vertical mixer according to certain charging sequence then and mix, vacuum pouring is put into baking oven curing 7-8 days after the pressurize degasification in mould, obtain the COMPOSITE SOLID PROPELLANT piece of even compact.
Sampling, detection contains the catalytic efficiency of the propellant of each embodiment catalyst, sees table 1.
The catalytic efficiency of table 1 embodiment Preparation of Catalyst propellant
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | Blank |
| Fire fast mm/s | 60.51 | 70.39 | 80.51 | 69.48 | 74.15 | 68.45 | 13.20 |
Can find out from table 1, contain more than all high 45mm/s of combustion speed of propellant burning rate than blank formula of product of various embodiments of the present invention catalyst that show that it can be used as the burningrate catalyst of the high quick burning speed of fourth hydroxyl propellant, catalytic effect very significantly.
To contain in addition embodiment 1 the grafting of replacement ferrocene silane fourth hydroxyl burningrate catalyst and the blank propellant that do not contain catalyst alternately; After special clamps; Place 70 ℃ of oil bath baking ovens to store, sampling regularly detects the combustion speed of propellant and the variation of Fe content.
Performance test: adopt the underwateracoustic shooting method to test propellant medicinal strip combustion speed, one directional tensile test machine test mechanical properties of propellant, Haake viscosimeter test medicine is starched working life, the iron content of ultraviolet/visible/near infrared spectrometer test propellant.
Table 2 embodiment 1 product migration performance result of study
Can find out from table 2; The propellant burning rate that contains catalyst is being tested the trend that significantly decreases early stage; Tend towards stability gradually to the later stage, and the combustion of blank propellant speed rises earlier and afterwards tends towards stability, and explains in the storage process; Contain embodiment 3 product catalyst micro-migration has only taken place, and the variation of combustion speed has only 1.2%.
Table 3 embodiment 1 product propellant processing performance result of study (50 ℃)
Can find out that from table 3 the COMPOSITE SOLID PROPELLANT slurry viscosity and the yield value that contain embodiment 3 products are all little a lot of than blank, explain that it has long operating period and good rheological behavior, processing performance is fine.
Each raw material that the present invention is cited, and the bound value of each raw material, with and interval value, can both realize the present invention; And the bound value of each technological parameter (like temperature, time etc.), with and interval value, can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (10)
1. preparation method who replaces the fourth hydroxyl burningrate catalyst of ferrocene silane grafting is characterized in that comprising following concrete steps:
(1) with the zinc chloride be catalyst, carry out the chlorine alkylation modification with the chlorine alkyl ether to replacing ferrocene, single step reaction obtains the chlorine alkylation and replaces ferrocene;
(2) under the effect that iodine causes, above-mentioned chlorine alkylation replacement ferrocene and magnesium chips are reacted, add silylating reagent backflow preparation after reaction finishes and replace ferrocene silane;
(3) under the effect of transition-metal catalyst, replace the silicon hydrogenation of ferrocene silane and end hydroxy butadiene, the end hydroxy butadiene of preparation replacement ferrocene silane grafting promptly replaces the fourth hydroxyl burningrate catalyst of ferrocene silane grafting.
2. preparation method according to claim 1 is characterized in that: described replacement ferrocene is: the mixing of one or more in bromo ferrocene, iodo ferrocene, ferrocenecarboxylic acid, ferrocene amine, methyl ferrocene, ethyl dicyclopentadienyl iron, the propyl group ferrocene.
3. preparation method according to claim 1; It is characterized in that: described chlorine alkyl ether is: chloromethyl methyl ether, 2-chloroethyl methyl ether, 3-chloropropyl methyl ether, 4-chlorobutyl methyl ether, 1, the mixing of one or more in the 4-dichloro methyl butyl ether.
4. preparation method according to claim 1; It is characterized in that: the concrete steps of said step (1) are: in amount of substance; Replacing ferrocene with 1 part is dissolved in the solvent; Add 0.1-2 part chlorine alkyl ether, 0.01-0.1 part zinc chloride again, back flow reaction 2-24 hour, reaction finishes after washing, separatory, drying, revolve to steam and obtain the chlorine alkylation and replace ferrocene.
5. preparation method according to claim 1 is characterized in that: described silylating reagent is a chlorodimethyl silane.
6. preparation method according to claim 1 is characterized in that: the concrete steps of said step (2) are: in amount of substance, in the airtight reaction vessel that is full of nitrogen of drying, add dry solvent, 0.5-2 part magnesium chips; Add the alkylation of 0.1-0.5 part chlorine then and replace ferrocene, a little iodine crystalline substance; The low-grade fever initiation reaction, and then drip remaining chlorine alkylation replacement ferrocene, the total amount that the chlorine alkylation of twice dropping replaces ferrocene is 1 part; Back flow reaction 2-24 hour; The silylating reagent that then adds 0.5-2 part back flow reaction 2-24 hour, washing, separatory, revolves to steam and obtains replacing ferrocene silane.
7. preparation method according to claim 1 is characterized in that: the transition-metal catalyst of said step (3) is one or more the mixing in chloroplatinic acid, the triphenylphosphine radium chloride; Described end hydroxy butadiene molecular weight is 1000-8000.
8. preparation method according to claim 1; It is characterized in that: the concrete steps of said step (3) are: in amount of substance; In the reaction vessel of drying, add dry solvent; Add 0.001-0.01 part catalyst, drip the solution that contains 1 part of ferrocene silane and 0.01-0.1 part end hydroxy butadiene, dropwise the back can obtain the grafting of ferrocene silane after back flow reaction 2-24 hour in 30-110 ℃ of scope fourth hydroxyl burningrate catalyst.
9. preparation method according to claim 1 is characterized in that: the solvent in said step (1) or step (2) or the step (3) is one or more the mixing in carrene, chloroform, oxolane, dimethyl formamide, dimethylacetylamide, methyl-sulfoxide, the toluene.
10. replace the fourth hydroxyl burningrate catalyst of ferrocene silane grafting, it is characterized in that: it prepares according to the described preparation method of arbitrary claim among the claim 1-9.
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| CN103242377A (en) * | 2013-04-22 | 2013-08-14 | 苏州志向纺织科研股份有限公司 | Alpha,omega-biferrocene hydrocarbon and preparation method thereof |
| CN103242377B (en) * | 2013-04-22 | 2016-02-10 | 苏州志向纺织科研股份有限公司 | A kind of α, ω-di-ferrocene hydrocarbon and preparation method thereof |
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