CN108841178A - A kind of preparation method of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber - Google Patents
A kind of preparation method of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber Download PDFInfo
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- CN108841178A CN108841178A CN201810418153.6A CN201810418153A CN108841178A CN 108841178 A CN108841178 A CN 108841178A CN 201810418153 A CN201810418153 A CN 201810418153A CN 108841178 A CN108841178 A CN 108841178A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of preparation methods of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber, include the following steps：Step（1）, the hydroxy-end capped polymethyl siloxane of 100 parts by weight is mixed with the hydroxy-end capped liquid fluorosilicone rubber of 5 ~ 100 parts by weight, is stirred evenly, fluorine silica-gel mixture is made；Step（2）, by 2 ~ 15 parts by weight silicon titanium high temperature resistant additives and the phenyl methyl silicone oil of 2 ~ 50 parts by weight 15 ~ 90oIt is mixed under conditions of C, is added in fluorine silica-gel mixture, is uniformly dispersed after being uniformly dispersed, base rubber is made；Step（3）Under the conditions of nitrogen protection; 3 ~ 15 parts by weight phenyl tributanoximo silanes, 1 ~ 5 parts by weight silane coupling agent, 0.01 ~ 0.5 part by weight of catalyst are sequentially added into the base rubber; after stirring 0.5-3h; 0.1 ~ 1h is stirred under conditions of vacuum degree is greater than -0.095MPa, obtains room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber.Heat resistance greatly improves compared with existing RTV fluorocarbon silicone rubber, and the fluorine silicone rubber is aging 7 days under conditions of 350 DEG C, and mechanical performance is without significant change.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of room temperature vulcanization condensation de-oxime type high-temperature resistant one-component fluorine
The preparation method of silicon rubber.
Background technique
Organic fluorinated silicone rubber is a kind of silicon rubber, the fluorubber advantage of integrating as the novel elastomer material of the whole body.Siliceous high score
Sub- material has many advantages, such as high-low temperature resistant, resistance to ag(e)ing and self-extinguishment, and fluorine element electronegativity is strong, the C- being connected to carbon atom
F key is stablized, and heat resistance is also higher, and fluorine element is introduced into siloxanes, polysiloxanes can kept superior heat-resisting
On the basis of property, weatherability, hydrophobicity and release property, it is further introduced into waterproof, oil resistant and solvent resistant that fluorochemical has
The performances such as property.It can be widely used in the essential industries such as automobile, aircraft, aerospace, petrochemical industry, machinery, artificial organs department and neck
Domain is a kind of novel high polymer material indispensable in national defence and national economy.
Currently, the fluorine silicone rubber product used in industry is suitable for using between -60 DEG C ~ 250 DEG C more, if being more than this temperature
Range is spent, properties of product will be decayed.It is typically employed in the method that heat-resisting additive is added in rubber and improves the heat-resisting of rubber
Performance.It is a variety of by adding heat stabilizer in view of organic fluorinated silicone rubber and organic silicon rubber structure and characteristic have similitude
Or the method that the method for heat-resistant filler promotes organic silicon rubber heat resistance is equally applicable to organic fluorinated silicone rubber.Chinese patent
CN1912005A prepares de- acetone room temperature vulcanized silicone rubber using rare earth derivative as heat-resisting additive, and this method is equally applicable
Heat resistance is promoted in fluorine silicone rubber, but mechanical performance is lower after aging under the conditions of 300 DEG C for this method, is unable to meet demand.In
State invents CN101570680A and prepares dealcoholized type room temperature vulcanized silicone rubber, this method application using the heat-resisting effect of titanium dioxide
In fluorine silicone rubber system, mechanical performance decline is very fast after aging under the conditions of 300 DEG C for glue sample.CN104774334A discloses one
Kind can be used as the preparation method for the silicon titanium polymer that additive uses, and related silicon titanium polymer can have as high temperature resistant filler
Improve the high temperature resistance of silicon rubber in effect ground.
Summary of the invention
The invention discloses a kind of preparation methods of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber, include the following steps：
Step（1）, by the hydroxy-end capped polymethyl siloxane of 100 parts by weight and the hydroxy-end capped liquid fluorosilicone rubber of 5 ~ 100 parts by weight
It is mixed, is stirred evenly, fluorine silica-gel mixture is made.
Step（2）, by 2 ~ 15 parts by weight silicon titanium high temperature resistant additives and the phenyl methyl silicone oil of 2 ~ 50 parts by weight 15 ~
90oIt is mixed under conditions of C, is added in fluorine silica-gel mixture, is uniformly dispersed after being uniformly dispersed, base rubber is made.
Step（3）, under the conditions of nitrogen protection, 3 ~ 15 parts by weight phenyl tributanoximo silicon are sequentially added into base rubber
Alkane, 1 ~ 5 parts by weight silane coupling agent, 0.01 ~ 0.5 part by weight of catalyst, stir 0.5-3h after, vacuum degree be greater than-
0.1 ~ 1h is stirred under conditions of 0.095MPa, and room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber is made.
Silicon titanium high temperature resistant additive according to the present invention is silicon titanium hybridized polymer, and structural formula is：。
Hydroxyl endblocked polydimethylsiloxane structural formula according to the present invention is HO- [(CH3)2Si-O]n- H, at 25 DEG C
Under average viscosity be 5 ~ 100Pa.s.
Hydroxy-end capped liquid fluorosilicone rubber according to the present invention is hydroxy-end capped poly- methyl trifluoro propyl siloxanes, knot
Structure formula is HO- [CH3(CH2CH2CF3)Si-O]n- H, the average viscosity at 25 DEG C are 5 ~ 100Pa.s.
Silane coupling agent according to the present invention is gamma-amino propyl trimethoxy silicane, gamma-amino propyl triethoxy
Silane, γ-（2,3- the third oxygen of epoxy）One or more of mixtures of propyl trimethoxy silicane.
Catalyst according to the present invention is dibutyl tin dilaurate or dibutyltin diacetate.
Silicon titanium high temperature resistant additive according to the present invention is silicon titanium hybridized polymer, and also referred to as poly- silicon titanoxane refers to
Main chain is by three kinds of silicon, oxygen, titanium elements（Si-O-Ti）The elemento-organic polymer of composition.Because it introduces gold in organosilicon systems
Belong to element titanium after, Si-O-Ti bond energy be higher than Si-O-Si bond energy so that the heat resistance of silicon titanium hybridized polymer have it is very big
It improves, it had not only overcome the brittleness of inorganic material, but also increased the compatibility with organic fluorinated silicone system, greatly improved fluorine silicone rubber
High temperature resistance, be a kind of very effective filler for improving silicon-fluorine polymer object high temperature resistance.
The present invention is used cooperatively using the heatproofs filler such as sial hybridized polymer and aluminium oxide powder, efficiently solves room
The use problem of temperature vulcanization fluorine silicone rubber at high temperature, RTV fluorocarbon silicone rubber obtained is aging 7 days under the conditions of 350 DEG C
Afterwards, mechanical property reduces amplitude within 15%, smaller with difference before aging, therefore, room temperature vulcanization fluorine silicon prepared by the present invention
Rubber can work in 350 DEG C of high temperatures, connect especially suitable for automobile engine, aeroengine, missile propulsion system etc.
Touch the sealing under fuel oil, contact hot conditions.
Detailed description of the invention
Fig. 1 is the main performance index of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber prepared by embodiment 1.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below.
Embodiment 1：
Present embodiments provide a kind of preparation method of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber, a kind of related room temperature
Vulcanize high-temperature resistant one-component fluorine silicone rubber based on parts by weight, component is as follows：Hydroxyl endblocked polydimethylsiloxane（Jiangxi is blue
Star fire organosilicon company produces 107 glue, viscosity 10500mm2/s）100 parts；Hydroxy-end capped liquid fluorosilicone rubber（Changchun is uncommon
The production of Lactel new material Co., Ltd, trade names FS-1601, viscosity 15000mm2/s）100 parts；The addition of silicon titanium high temperature resistant
Agent（The production of Changchun Shiran spy's new material Co., Ltd, trade names AS-1509）10 parts；Phenyl methyl silicone oil（Changchun Shiran is special
The production of new material Co., Ltd, trade names XLT-1301, viscosity 5000mm2/s）50 parts；Alumina powder（Partial size is 30-
50nm）60 parts；10 parts of phenyl tributanoximo silane；2 parts of gamma-amino propyl trimethoxy silicane；Dibutyl tin dilaurate
0.1 part.
The specific preparation method of above-mentioned high-temperature resistant single-component room temperature vulcanized silicone rubber provided in this embodiment is：By 100 parts
Obtained fluorine silica gel mixing is mixed evenly in hydroxyl endblocked polydimethylsiloxane and 100 parts of hydroxy-end capped liquid fluorosilicone rubbers
Object.By 10 parts of silicon titanium high temperature resistant additives and 50 parts of phenyl methyl silicone oil 60oIt is mixed, is uniformly dispersed under conditions of C
After be added in fluorine silica-gel mixture, be uniformly dispersed, be made base rubber.Under the conditions of nitrogen protection, 10 are sequentially added into base rubber
Part phenyl tributanoximo silane, 2 parts of gamma-amino propyl trimethoxy silicanes, 0.1 part of dibutyl tin dilaurate, stir 2h
Afterwards, 0.5h is stirred under conditions of vacuum degree is greater than -0.095MPa, obtains high-temperature resistant single-component RTV fluorocarbon silicone rubber.
The main performance index of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber prepared by embodiment 1 is shown in Fig. 1.
Claims (6)
1. a kind of preparation method of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber according to the present invention, includes the following steps：
Step（1）, the hydroxy-end capped polymethyl siloxane of 100 parts by weight and the hydroxy-end capped liquid fluorosilicone rubber of 5 ~ 100 parts by weight are carried out
Mixing, stirs evenly, and fluorine silica-gel mixture is made；Step（2）, by 2 ~ 15 parts by weight silicon titanium high temperature resistant additives and 2 ~ 50 weight
The phenyl methyl silicone oil of part is 15 ~ 90oIt is mixed, is added to after being uniformly dispersed in fluorine silica-gel mixture under conditions of C, dispersed
Uniformly, base rubber is made；Step（3）, under the conditions of nitrogen protection, 3 ~ 15 parts by weight phenyl, three diacetylmonoxime is sequentially added into base rubber
Base silane, 1 ~ 5 parts by weight silane coupling agent, 0.01 ~ 0.5 part by weight of catalyst, stir 0.5-3h after, vacuum degree be greater than-
0.1 ~ 1h is stirred under conditions of 0.095MPa, and room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber is made.
2. silicon titanium high temperature resistant additive described in claim 1 is silicon titanium hybridized polymer, structural formula is：。
3. hydroxyl endblocked polydimethylsiloxane structural formula described in claim 1 is HO- [(CH3)2Si-O]n- H, at 25 DEG C
Under average viscosity be 5 ~ 100Pa.s.
4. hydroxy-end capped liquid fluorosilicone rubber described in claim 1 is hydroxy-end capped poly- methyl trifluoro propyl siloxanes, knot
Structure formula is HO- [CH3(CH2CH2CF3)Si-O]n- H, the average viscosity at 25 DEG C are 5 ~ 100Pa.s.
5. silane coupling agent described in claim 1 is gamma-amino propyl trimethoxy silicane, gamma-amino propyl triethoxy
Silane, γ-（2,3- the third oxygen of epoxy）One or more of mixtures of propyl trimethoxy silicane.
6. catalyst described in claim 1 is dibutyl tin dilaurate or dibutyltin diacetate.
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| CN201810418153.6A CN108841178A (en) | 2018-05-04 | 2018-05-04 | A kind of preparation method of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber |
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| CN201810418153.6A CN108841178A (en) | 2018-05-04 | 2018-05-04 | A kind of preparation method of room temperature vulcanization high-temperature resistant one-component fluorine silicone rubber |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118027887A (en) * | 2024-04-12 | 2024-05-14 | 有行鲨鱼（上海）科技股份有限公司 | Single-component silicone plane sealant for automobile and preparation method thereof |
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2018
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| DE69521539T2 (en) * | 1994-02-25 | 2002-04-04 | Dow Corning Asia Ltd | Process for the preparation of polytitanosiloxanes which are soluble in organic solvents |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118027887A (en) * | 2024-04-12 | 2024-05-14 | 有行鲨鱼（上海）科技股份有限公司 | Single-component silicone plane sealant for automobile and preparation method thereof |
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