CN104829838B - A kind of preparation method of hydroxy-end capped poly- fluorosilicone - Google Patents
A kind of preparation method of hydroxy-end capped poly- fluorosilicone Download PDFInfo
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- CN104829838B CN104829838B CN201510226525.1A CN201510226525A CN104829838B CN 104829838 B CN104829838 B CN 104829838B CN 201510226525 A CN201510226525 A CN 201510226525A CN 104829838 B CN104829838 B CN 104829838B
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Abstract
The present invention relates to a kind of preparation method of hydroxy-end capped poly- fluorosilicone; specifically under room temperature inert gas shielding trifluoro propyl methyl cyclotrisiloxane is caused to carry out anionic ring-opening polymerization as non-equilibrium property initiator with diphenyl silanediol lithium; react constant to viscosity; end-capping reagent water, removed under reduced pressure low boiling is added to obtain hydroxy-end capped poly- fluorosilicone.The present invention controls the molecular weight of product using initiator amount, molecular weight of product poor controllability caused by water institute incompatible with reaction system is solved the problems, such as, and non-equilibrium property initiator can effectively suppress " return and sting " and " redistribution " side reaction during anionic ring-opening polymerization.The hydroxy-end capped poly- fluorosilicone molecular weight for preparing of the invention is controllable, narrow molecular weight distribution, quality stable homogeneous.Using this product as liquid fluorosilicone rubber rubber, the oil resistant field of sealing technology of military and civilian etc. is can be widely applied to, with good economic benefit and promotional value.
Description
Technical field
The invention belongs to technical field of chemistry, is related to a kind of preparation method of hydroxy-end capped poly- fluorosilicone.
Background technology
Hydroxy-end capped poly- fluorosilicone, structural formulaAs the rubber of liquid fluorosilicone rubber, molecular structure
In trifluoropropyl group give the excellent resistance to fuel oil of fluorosioloxane rubber, high and low temperature resistance, and liquid fluorosilicone rubber is in room temperature
Under the conditions of can sulfuration, so more convenient compared to the processing of solid fluorosioloxane rubber, range of application is wider, can preferably be applied to me
The oil resistant field of sealing technology of state's national defence, aviation etc..
The preparation of hydroxy-end capped poly- fluorosilicone typically adopts methyl trifluoro propyl cyclotrisiloxane (D3F) draw in balance
Anionic ring-opening polymerization is carried out under the catalysis of the silicon alkoxide for sending out agent NaOH, potassium hydroxide or TMAH, such as
Patent CN 101376709A.On the one hand, the strong electrophilic inductive effect of trifluoro propyl causes D3The anionic ring-opening polymerization speed of F
Degree is fast, there is strong " inventing a charge against " and " redistribution " side reaction in polymerization process, is sufficiently achieving equilibrium stage, its linear poly- silicon
Oxygen alkane proportion is only 10～20%, causes polymerizate heterogeneity, molecular weight distribution width；On the other hand, after polymerisation
Phase system viscosity is big, end-capping reagent H2O causes to block effect on driving birds is not good with the incompatibility of polymerization system, and molecular weight poor controllability is produced
Quality is unstable.
The content of the invention
To solve the above problems, the invention provides a kind of preparation method of hydroxy-end capped poly- fluorosilicone, the preparation work
Skill is simple, molecular weight product is controllable, narrow molecular weight distribution, be suitable to industrialization promotion.
The technical solution used in the present invention is as follows：
A kind of preparation method of hydroxy-end capped poly- fluorosilicone, comprises the steps：
(1) polymerization process：Under inert gas shielding, non-equilibrium after trifluoro propyl methyl cyclotrisiloxane decompression dehydration
Property anion ring opening initiator initiation under carry out anionic ring-opening polymerization, controlling reaction temperature is 25～80 DEG C, until reaction
System viscosity is constant；
(2) capping process：After reaction system viscosity is constant, end-capping reagent H is added2O, continues 2～8h of reaction；
(3) take off low boiling process：Reaction system is warming up to 120 DEG C～180 DEG C under reduced pressure, remove low-boiling-point substance, the time be 1～
3h, obtains final product water white hydroxy-end capped poly- fluorosilicone.
Preferably, in step (1), described non-equilibrium property anion ring opening initiator is diphenyl silanediol lithium, is tied
Structure formula is
Preferably, in step (1), the described design molecular weight calculation according to hydroxy-end capped poly- fluorosilicone is calculated
Formula is:Consumption=228 of unbalanced type anionic initiator × m/M, wherein, m is trifluoro propyl methyl cyclotrisiloxane
Quality, M are the molecular weight of hydroxy-end capped poly- fluorosilicone.
Preferably, in step (2), described end-capping reagent H2The consumption of O is trifluoro propyl methyl cyclotrisiloxane quality
0.1%～1%.
Preferably, in step (3), after the reduced pressure treatment, the pressure condition of reaction system is 133～1330Pa.
Preferably, in step (3), described heating rate is 1～10 DEG C/min.
Preferably, the molecular weight of hydroxy-end capped poly- fluorosilicone prepared by said method is 103～105。
The hydroxy-end capped poly- fluorosilicone prepared using the preparation method of the hydroxy-end capped poly- fluorosilicone of the present invention.
Hydroxy-end capped poly- fluorosilicone prepared by the method for the invention can be used for the preparation of liquid fluorosilicone rubber.
The preparation method of the hydroxy-end capped poly- fluorosilicone of the present invention, using D3F is monomer, is urged in diphenyl silanediol lithium
Ring-opening polymerisation is carried out under change, the molecular weight of hydroxy-end capped poly- fluorosilicone is controlled by the consumption of initiator, molecule can be obtained
Measure 103～105In the range of adjustable narrow molecular weight distribution, the product of product quality stable homogeneous, and preparation process is simple fits
For industrialization promotion.
Beneficial effects of the present invention：
1. non-equilibrium property initiator inhibits D3" inventing a charge against " and " redistribution " side reaction in F anion ring opening process, makes
Molecular weight of product narrowly distributing, product stable homogeneous.
2. the molecular weight of hydroxy-end capped poly- fluorosilicone is controlled by the consumption of non-equilibrium property initiator, end-capping reagent is solved
H2The caused problem that molecular weight is uncontrollable, product batches are unstable of O and system incompatibility institute.
3. D is caused using non-equilibrium property initiator3F anionic ring-opening polymerizations, the neutralization for eliminating initiator were post-processed
Journey, simplifies production technology.
4. at room temperature, non-equilibrium property initiator causes D3F anionic ring-opening polymerizations, it is energy-saving, push away beneficial to industrialization
Extensively.
Description of the drawings
The hydroxy-end capped poly- fluorosilicones of Fig. 11H NMR
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.In embodiment, unless otherwise stated,
Otherwise all parts and percentages are on the basis of weight.
Experimental technique
The synthesis of diphenyl silanediol lithium
Under nitrogen protection, 8.4g lithium hydroxides are added with water knockout drum, condenser and machine with 21.6g diphenyl silanediols
In four mouthfuls of reaction bulbs of tool stirring, the mixed solvent 500g (m/m=1/1) of absolute ethyl alcohol and hexamethylene is added, 80 DEG C are heated to
System flows back, and ensures that the water for generating is separated from system in time in course of reaction, isothermal reaction 24h, and desolvation obtains faint yellow
Pressed powder 28.1g, yield 93.7%, sealing nitrogen charging are preserved, as D3F anionic ring-opening polymerization initiators.
The molecular weight of hydroxy-end capped poly- fluorosilicone using proton nmr spectra (1H NMR) determine, as a result such as Fig. 1, relatively
Molecular weight and molecular weight distribution are determined using gel permeation chromatography (GPC), solvent：Tetrahydrofuran.
Embodiment 1
By 1000g D3F is added in polymeric kettle, is warming up to 40 DEG C, and 1h, drying nitrogen ventilation 3 are dehydrated under 0.01MPa
Room temperature is down to after secondary, diphenyl silanediol lithium 7.60g is added, is stirred, controlling reaction temperature is 25～80 DEG C, system viscosity
It is slowly increased, is polymerized constant to reaction system viscosity, adds 5.0g end-capping reagent H2Continue reaction 4h after O, then reduce pressure 400Pa,
5 DEG C/min of programming rate is warming up to 150 DEG C, removes low-boiling-point substance 2h, and water white hydroxy-end capped poly- fluorosilicone, drop is obtained
Temperature, discharging, product1H NMR are as shown in figure 1, the molecular weight and its distribution results of product are listed in table 1.
Embodiment 2
Repeat the step described in embodiment 1, simply add diphenyl silanediol lithium 22.8g.The molecular weight of product and its point
Cloth result is listed in table 1.
Embodiment 3
Repeat the step described in embodiment 1, simply add diphenyl silanediol lithium 4.56g.The molecular weight of product and its point
Cloth result is listed in table 1.
Embodiment 4
Repeat the step described in embodiment 1, simply add diphenyl silanediol lithium 45.6g.The molecular weight of product and its point
Cloth result is listed in table 1.
Embodiment 5
Repeat the step described in embodiment 1, simply add H2O 2.0g.The molecular weight and its distribution results of product is listed in table
1。
Embodiment 6
Repeat the step described in embodiment 1, simply add H2O 10.0g.The molecular weight and its distribution results of product is listed in
Table 1.
Comparative example 1
Repeat the step described in embodiment 1, simply molecular weight of product end-capping reagent H in polymerization process2O is controlled, H2The use of O
Measure as 0.6g, catalyst uses NaOH silicon alkoxide.The molecular weight and its distribution results of product is listed in table 1.
Comparative example 2
Repeat the step described in embodiment 1, simply molecular weight of product end-capping reagent H in polymerization process2O is controlled, H2The use of O
Measure as 0.6g, catalyst uses TMAH silicon alkoxide.The molecular weight and its distribution results of product is listed in table 1.
Comparative example 3
Repeat the step described in embodiment 1, simply molecular weight of product end-capping reagent H in polymerization process2O is controlled, H2The use of O
Measure as 0.6g, catalyst uses potassium hydroxide silicon alkoxide.The molecular weight and its distribution results of product is listed in table 1.
The measurement result of the hydroxy-end capped poly- fluorosilicone molecular weight of table 1 and molecular weight distribution
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to present invention protection model
The restriction enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not
The various modifications made by needing to pay creative work or deformation are still within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of hydroxy-end capped poly- fluorosilicone, is characterized in that, comprise the steps：
(1) polymerization process：It is under inert gas shielding, cloudy in non-equilibrium property after trifluoro propyl methyl cyclotrisiloxane decompression dehydration
Anionic ring-opening polymerization is carried out under the initiation of ion ring opening initiator, described non-equilibrium property anion ring opening initiator is hexichol
Base silicon diol lithium, structural formula isControlling reaction temperature is 25～80 DEG C, until reaction system viscosity is constant；
(2) capping process：After reaction system viscosity is constant, end-capping reagent H is added2O, continues 2～8h of reaction；
(3) take off low boiling process：Reaction system is warming up to 120 DEG C～180 DEG C under reduced pressure, removes low-boiling-point substance, and the time is 1～3h,
Obtain final product water white hydroxy-end capped poly- fluorosilicone.
2. in the preparation method of hydroxy-end capped poly- fluorosilicone according to claim 1, it is characterised in that：It is described non-equilibrium
Consumption=228 of type anionic initiator × m/M, wherein, m is the quality of the trifluoro propyl methyl cyclotrisiloxane, and M is institute
State the molecular weight of hydroxy-end capped poly- fluorosilicone.
3. in the preparation method of hydroxy-end capped poly- fluorosilicone according to claim 1, it is characterised in that：In step (2),
Described end-capping reagent H2The consumption of O for trifluoro propyl methyl cyclotrisiloxane quality 0.1%～1%.
4. in the preparation method of hydroxy-end capped poly- fluorosilicone according to claim 1, it is characterised in that：In step (3),
After the reduced pressure treatment, the pressure condition of reaction system is 133～1330Pa.
5. in the preparation method of hydroxy-end capped poly- fluorosilicone according to claim 1, it is characterised in that：In step (3),
Described heating rate is 1～10 DEG C/min.
6. in the preparation method of hydroxy-end capped poly- fluorosilicone according to claim 1, it is characterised in that：Described hydroxyl
The molecular weight for blocking poly- fluorosilicone is 103～105。
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| CN105348537B (en) * | 2015-10-27 | 2018-07-31 | 浙江理工大学 | A kind of fluorine functional silicon macromonomer of the single-ended double bond containing alkene and preparation method thereof |
| CN106349277B (en) * | 2016-08-24 | 2019-03-26 | 山东大学 | A method of preparing alkoxy end-capped poly- methyl trifluoro propyl siloxane oligomer |
| CN109851786A (en) * | 2017-11-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | A kind of fluorine silicon rubber base glue and preparation method thereof |
| CN109851787A (en) * | 2017-11-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | A kind of fluorine silicon rubber base glue and preparation method thereof |
| CN111635503B (en) * | 2020-06-29 | 2023-03-17 | 浙江福斯特新材料研究院有限公司 | Fluorosilicone modified epoxy resin, preparation method and application thereof |
| CN113881029B (en) * | 2021-10-09 | 2023-05-26 | 万华化学集团股份有限公司 | Polysiloxane-terminated modified copolycarbonate and preparation method thereof |
| CN115819773B (en) * | 2022-05-27 | 2023-10-03 | 浙江开化合成材料有限公司 | Preparation method of high-temperature-resistant benzyl silicone oil with narrow molecular weight distribution |
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| CN104119535A (en) * | 2014-03-06 | 2014-10-29 | 杭州师范大学 | Preparation method of hydroxyl-terminated fluorosilicone crude rubber |
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| EP0317840A1 (en) * | 1987-11-25 | 1989-05-31 | General Electric Company | Catalyst for producing fluorosilicone polymers |
| CN1303879A (en) * | 1999-11-23 | 2001-07-18 | 中国科学院化学研究所 | Cyclosiloxane anion non-equilibrium ring-opening polymerization method |
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