CN106397770B - A kind of fluoropolymer, cross-linking agent and its preparation and application - Google Patents
A kind of fluoropolymer, cross-linking agent and its preparation and application Download PDFInfo
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- CN106397770B CN106397770B CN201610862281.0A CN201610862281A CN106397770B CN 106397770 B CN106397770 B CN 106397770B CN 201610862281 A CN201610862281 A CN 201610862281A CN 106397770 B CN106397770 B CN 106397770B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/24—Copolymers of a fluoronitroso organic compound and another fluoro organic compound, e.g. nitroso rubbers
- C08G73/26—Copolymers of a fluoronitroso organic compound and another fluoro organic compound, e.g. nitroso rubbers of trifluoronitrosomethane with a fluoro-olefin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1009—Fluorinated polymers, e.g. PTFE
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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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
- C08L2312/00—Crosslinking
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention provides one kind with as follows（I）Fluoropolymer, cross-linking agent and its preparation and application of shown molecular structure,
Description
Technical field
The present invention relates to a kind of fluorinated polymer material, especially a kind of carboxyl nitroso fluoropolymer, cross-linking agent and
Its preparation and application belongs to organic fluorine chemistry technology or polymer material field.
Background technology
Carboxyl nitroso fluoropolymer（Carboxyl Nitroso Rubber, abbreviation CNR）It is by nitroso fluoroform
A kind of fluoropolymer that alkane, tetrafluoroethene, γ-Trifluoronitrosomethane and Nitrosoperfluorobutyric acid are copolymerized at low temperature.CNR high polymer main chains one
Half is carbon-carbon bond（-C-C-）, the other half is nitrogen-oxygen bond（-N-O-）, and be all replaced by fluorine atoms with the carbon atom proton that is connected, have
Good chemical stability；The a large amount of nitrogen oxygen chain link of main chain assigns rubber excellent resistance to low temperature.It is being same with the present invention
It is fluorine-containing poly- that high and low molecular weight carboxyl nitroso is described in patent CN102731784B, CN103214613B of applicant respectively
The process of preparing of object is closed, patent CN102746666B, CN103965823B, CN103980772B, CN103980702B are then
Describe method for processing forming and the application of carboxyl nitrsofluoro rubber.
Carboxyl nitrsofluoro rubber is due to its special powerful oxidation corrosion resistance medium（That is medium tolerance）And resistance to low temperature,
It is the indispensable sealing material of field of aerospace, is widely applied in the transmitting of liquid Future Launch Rocket.But carboxyl
Nitroso fluoropolymer is as a kind of excellent media-resistant, low temperature resistant of having both simultaneously（Glass transition temperature≤- 45 DEG C）Performance
Fluorine material, current application still is limited to aerospace field.In view of the performance characteristics that such polymer has itself,
It should be able to meet in other fields, such as the requirement of chemical industry, electronics and new energy numerous areas.For this purpose, of the invention
On the basis of above-mentioned existing patented technology, by using the high reaction activity feature of carboxyl, prepare a kind of novel
Fluoropolymer to further expand the application field of such polymer, and achieves good technique effect, the technology
Relevant report that at home and abroad so far there are no.
Invention content
The present invention is to provide a kind of nitroso containing phenyl boric acid on the basis of using the high reaction activity feature of carboxyl
Fluoropolymer, cross-linking agent and its preparation and application.The fluoropolymer can not only realize that phenyl boric acid is converted to the crosslinking of borine
Molding, and the crosslinking of borine solution can be made to be changed into boric acid again under hydrone effect, phenyl boric acid can again be realized again to borine conversion
Secondary cross moulding, i.e. fluoropolymer obtain repeated multiple times application, have opened up the fluoropolymer-containing application prospect of carboxyl nitroso.
For achieving the above object, the technical solution adopted by the present invention is as follows：
A kind of fluoropolymer, it is characterised in that have as follows（I）Shown in molecular structure：
Wherein R represents the free radicals group such as proton H or low carbon chain alkyl；X represents amide or ester bond equivalence bond structure list
Member；Main polymer chain is the repetitive unit of nitroso-tetrafluoroethene, and side chain passes through amide or ester bond equivalence key connecting phenyl boric acid list
Member；M and n represent the degree of polymerization.
Preferably, described（I）Shown in R in molecular structure represent proton H.
The low carbon chain alkyl is selected from the alkyl of C1~C5, such as-CH3、-CH2CH3Deng preferably methyl-CH3。
It is described（I）The fluoropolymer of shown molecular structure be by（III）The carboxyl nitroso fluoropolymer of shown structure
Object with（IV）The phenyl boric acid of shown structure, passes through（II）It is prepared by the shown reaction mechanism mechanism of reaction：
Wherein（III）The carboxyl nitroso fluoropolymer of shown structure carries carboxyl-reactive structural unit,（IV）It is shown
The phenyl boric acid of structure is with reaction active groups such as amino or hydroxyls.
It is described（III）The carboxyl nitroso fluoropolymer of shown structure is nitroso fluoroform, tetrafluoroethene and γ-
The terpolymer of Trifluoronitrosomethane and Nitrosoperfluorobutyric acid, the polymer carboxyl mole percent are 0.5~1.5%, and mole percent is preferred
0.7~1.2%.
Fluoropolymer cross-linking agent of the present invention be pass through by（I）The fluoropolymer-containing side chain phenyl boric acid of shown molecular structure
Change crosslinking to borine and formed, the borine of cross-linking agent can then solve crosslinking under hydrone effect and be changed into boric acid, and phenyl boric acid turns
Cross moulding again can be realized again by being changed to borine.So that fluoropolymer has reached repeated multiple times application.
The present invention（I）The fluoropolymer of shown molecular structure can also add auxiliary addition agent or benefit when being crosslinked
Strong filler etc..
The auxiliary addition agent may include：Accelerating agent, levelling agent etc..
The reinforced filling is selected from whisker, carbon fiber or white carbon etc., preferably through the high-reinforcement white carbon black of hydrophobic treatment.
It is described（III）The carboxyl nitroso fluoropolymer of shown structure is prepared using solution polymerization process, specifically
To be prepared according to the solution polymerization process described in patent CN102731784B or CN103214613B.
It is described（IV）The preferred 3- amino phenyl boric acid of phenyl boric acid of shown structure, 4- amino phenyl boric acid, 3- hydroxyls phenyl boric acid or
The phenyl boric acids with active group such as 4- hydroxyl phenyl boric acids can be one or any two or more combination.
It is of the present invention（I）The fluoropolymer of shown molecular structure is that bulk process or solution methods is taken to be reacted
It prepares, concrete operation step is as follows：
--- when carrying out reaction preparation with solution methods, first will be（III）The carboxyl nitroso fluoropolymer of shown structure
Object is dissolved in fluorochlorohydrocarbon and is formulated as solution, is then added again into solution（IV）The phenyl boric acid of shown structure, in stirring, 50~80
2~5h is reacted at a temperature of DEG C to obtain（I）The fluoropolymer product of shown molecular structure.The reaction product divides water by standing
Afterwards, it can directly use in the form of a solution, may also pass through after concentration extracts solvent and use.
The fluorochlorohydrocarbon is selected from trifluorotrichloroethane（F113）Or perfluoroparaffin；The perfluoroparaffin such as perfluorotributylamine, perfluor
Triethylamine etc..
It is described（III）The carboxyl nitroso fluoropolymer of shown structure is formulated as a concentration of 5~30wt% of solution.
It is described（IV）The phenyl boric acid of shown structure with（III）The carboxyl nitroso fluoropolymer carboxyl of shown structure rubs
Your ratio is 1.05~1:1.
--- when being prepared using bulk reaction method, be by（III）The low-molecular-weight liquid carboxyl of shown structure is sub-
Nitro fluoropolymer is directly same（IV）The phenyl boric acid of shown structure carries out bulk reaction and is prepared（I）Shown molecular structure
Fluoropolymer product；It is described（IV）The phenyl boric acid of shown structure with（III）The carboxyl nitroso fluoropolymer of shown structure
The molar ratio of carboxyl is 1.05~1:1, the reaction time is 2~5h, and reaction temperature is controlled at 50~80 DEG C.For the benefit of react
It carries out, can be by theoretical 3~5 times of addition azeotropic dehydrating agents for generating water volume in reaction, or carry out vacuum and extract dehydration.
The azeotropic dehydrating agent includes：Benzene, toluene etc..
The fluoropolymer-containing inherent viscosity ＜ 0.3dL/g of low-molecular-weight liquid carboxyl nitroso, carboxyl-content >=
0.5mol%。
The present invention（I）The fluoropolymer of shown molecular structure can be used as the uses such as adhesive, sealing material.
The beneficial effects of the present invention are：
1, provided by the invention（I）The fluoropolymer of shown molecular structure can be changed by side chain phenyl boric acid to borine
Realize that cross moulding, borine can then solve crosslinking under hydrone effect and be changed into boric acid, phenyl boric acid is converted to borine and can be realized again
Cross moulding again so that fluoropolymer has reached repeated multiple times application.
2, provided by the invention（I）The fluoropolymer of shown molecular structure uses（III）The carboxyl nitrous of shown structure
Base fluoropolymer with（IV）The phenyl boric acid of shown structure, is prepared by bulk reaction or solution reaction, and this method has
Simple for process, the reaction time is short, and environmental pollution is small, the advantages such as good product quality, it is easy to accomplish industrialized production.
3, of the invention（III）The carboxyl nitroso fluoropolymer raw material of shown structure, according to the existing patent of applicant
Solution polymerization process described in CN102731784B or CN103214613B is prepared, it can be achieved that solid forms high molecular weight
Carboxyl nitroso fluoropolymer, the fluoropolymer-containing synthesis of low-molecular-weight liquid carboxyl nitroso, technical maturity, yield and pure
Degree is high, and easy to operate, easy to implement, increases investment without additional.
4, of the invention（I）The control of carboxyl mole percent is 0.5~1.5% in the fluoropolymer of shown molecular structure, both
Enough cross moulding active sites can be provided, while also having preferable cost control.
5, due to the present invention（I）The fluoropolymer cross-linking agent of shown molecular structure, is to pass through（I）Shown molecular structure
Fluoropolymer-containing side chain phenyl boric acid changes crosslinking to borine and is formed, and the borine of the cross-linking agent solves crosslinking under hydrone effect
It is changed into boric acid, phenyl boric acid is converted to borine and realizes cross moulding again again, therefore the fluoropolymer is used as adhesive or close
Closure material is well positioned to meet in addition to aerospace field, such as chemical industry, electronics and new energy numerous areas requirement,
To further expand the application field of such polymer.
Specific implementation mode
The present invention is further described specifically by the following examples.It is necessarily pointed out that following implement
Example is served only for that the present invention is described further, should not be understood as limiting the scope of the invention, the field technology is ripe
Practice personnel and some nonessential modifications and adaptations are made to the present invention according to aforementioned present invention content, still falls within the protection of the present invention
Range.
Embodiment 1
It is 0.5dL/g, the solid forms high molecular weight carboxyl nitrous that carboxyl mole percent is 0.6% by 10g inherent viscosities
Base fluoropolymer（Structure is such as（III）It is shown）It is dissolved in trifluorotrichloroethane（F113）In be made into mass concentration be 10% it is molten
Then 3- amino phenyl boric acids are added in liquid into solution again（Structure is such as（IV）It is shown）0.2g reacts 5h at a temperature of stirring, 50 DEG C
Reaction was completed, and rotary evaporation removal solvent obtains fluoropolymer solids product.Product is shown through infrared analysis：Wave number exists
Carboxyl vibration absorption peak disappears at 1712cm-1, amide group absorption peak occurs in 1680cm-1,3515cm-1, in 1600cm-
1,2855cm-1, there is phenyl ring, borate absorption peak respectively in 2925cm-1, illustrates that carboxyl react transformation for mesh with amino
Mark product.
Embodiment 2
It is 0.5dL/g by 50g inherent viscosities, the solid forms high molecular weight carboxyl that carboxyl mole percent is 0.6% is sub-
Nitro fluoropolymer（Structure is such as（III）It is shown）It is dissolved in and is made into the solution that mass concentration is 20% in perfluoro triethylamine, then
3- amino phenyl boric acids are added into solution again（Structure is such as（IV）It is shown）1.1g, reaction 3h terminates anti-at a temperature of stirring, 60 DEG C
It answers, removal solvent obtains amber solid fluoropolymer product.Product is shown through infrared analysis：Wave number carboxylic at 1712cm-1
Base vibration absorption peak disappears, and amide group absorption peak occurs in 1680cm-1,3515cm-1, in 1600cm-1,2855cm-1,
There is phenyl ring, borate absorption peak respectively in 2925cm-1, illustrates that carboxyl react transformation for target product with amino.
Embodiment 3
It is 0.55dL/g by 50g inherent viscosities, the solid forms high molecular weight carboxyl that carboxyl mole percent is 1.2% is sub-
Nitro fluoropolymer（Structure is such as（III）It is shown）It is dissolved in and is made into the solution that mass concentration is 30% in perfluoro triethylamine, then
4- amino phenyl boric acids are added into solution again（Structure is such as（IV）It is shown）1.95g, reaction 2h terminates anti-at a temperature of stirring, 80 DEG C
It answers, obtains light yellow homogeneous fluoropolymer solutions product.Infrared analysis is shown：Wave number carboxyl absorption of vibrations at 1712cm-1
Peak disappears, and amide group absorption peak occurs in 1681cm-1,3515cm-1, distinguishes in 1600cm-1,2856cm-1,2928cm-1
There is phenyl ring, borate absorption peak, illustrates that carboxyl react transformation for target product with amino.
Embodiment 4
It is 0.55dL/g by 50g inherent viscosities, the solid forms high molecular weight carboxyl that carboxyl mole percent is 0.7% is sub-
Nitro fluoropolymer（Structure is such as（III）It is shown）It is dissolved in and is made into the solution that mass concentration is 5% in perfluorotributylamine, then
4- hydroxyl phenyl boric acids are added into solution again（Structure is such as（IV）It is shown）1.15g, reaction 5h terminates anti-at a temperature of stirring, 70 DEG C
It answers, removal solvent obtains light yellow fluoropolymer solids product.Infrared analysis is shown：Wave number carboxyl at 1712cm-1 vibrates
Absorption peak disappears, and occurs ester bond absorption peak at 1738cm-1, is 1600cm-1,2855cm-1,2925cm-1 difference in wave number
There is phenyl ring, borate absorption peak, illustrates that carboxyl react transformation for target product with phenolic hydroxyl group.
Embodiment 5
It is 0.45dL/g by 50g inherent viscosities, the solid forms high molecular weight carboxyl that carboxyl mole percent is 1.5% is sub-
Nitro fluoropolymer（Structure is such as（III）It is shown）It is dissolved in and is made into the solution that mass concentration is 15% in perfluoro triethylamine, then
3- hydroxyl phenyl boric acids are added into solution again（Structure is such as（IV）It is shown）2.5g, reaction 4h terminates anti-at a temperature of stirring, 60 DEG C
It answers, rotary evaporation removal solvent obtains light yellow fluoropolymer solids product.Infrared analysis is shown：Wave number is at 1715cm-1
Carboxyl vibration absorption peak disappear, occur ester bond absorption peak at 1740cm-1, wave number be 1601cm-1,2857cm-1,
There is phenyl ring, borate absorption peak respectively in 2926cm-1, illustrates that carboxyl react transformation for target product with phenolic hydroxyl group.
Embodiment 6
It is 0.1dL/g by 15g inherent viscosities, the low-molecular-weight liquid carboxyl nitroso that carboxyl mole percent is 1.0% contains
Fluoropolymer（Structure is such as（III）It is shown）Directly with 4- amino phenyl boric acids（Structure is such as（IV）It is shown）0.5g reacts（That is 4- amino
The molar ratio of phenyl boric acid and carboxyl nitroso fluoropolymer carboxyl is 1.05:1）, reaction 5h knots at a temperature of stirring, 80 DEG C
Shu Fanying obtains light yellow liquid fluorinated polymer product.Infrared analysis is shown：Wave number carboxyl absorption of vibrations at 1712cm-1
Peak disappears, and amide group absorption peak occurs in 1680cm-1,3515cm-1, distinguishes in 1600cm-1,2856cm-1,2928cm-1
There is phenyl ring, borate absorption peak, illustrates that carboxyl react transformation for target product with amino.
Embodiment 7
It is 0.08dL/g, the low-molecular-weight liquid carboxyl nitroso that carboxyl mole percent is 1.2% by 50g inherent viscosities
Fluoropolymer（Structure is such as（III）It is shown）Directly with 3- amino phenyl boric acids（Structure is such as（IV）It is shown）1.9g reaction（That is 3- ammonia
The molar ratio of base phenyl boric acid and carboxyl nitroso fluoropolymer carboxyl is 1:1）, reaction 4h knots at a temperature of stirring, 80 DEG C
Shu Fanying obtains light yellow liquid fluorinated polymer product.Infrared analysis is shown：Wave number carboxyl absorption of vibrations at 1712cm-1
Peak disappears, and amide group absorption peak occurs in 1680cm-1,3515cm-1, distinguishes in 1600cm-1,2857cm-1,2925cm-1
There is phenyl ring, borate absorption peak, illustrates that carboxyl react transformation for target product with amino.
Embodiment 8
It is 0.2dL/g by 15g inherent viscosities, the low-molecular-weight liquid carboxyl nitroso that carboxyl mole percent is 0.7% contains
Fluoropolymer（Structure is such as（III）It is shown）Directly with 4- hydroxyl phenyl boric acids（Structure is such as（IV）It is shown）0.34g reacts（That is 4- hydroxyls
The molar ratio of phenyl boric acid and carboxyl nitroso fluoropolymer carboxyl is 1.03:1）, reaction 3h knots at a temperature of stirring, 50 DEG C
Shu Fanying obtains light yellow liquid fluorinated polymer product.Infrared analysis is shown：Wave number carboxyl absorption of vibrations at 1712cm-1
Peak disappear, there is ester linkage group absorption peak in 1739cm-1,1598cm-1,2851cm-1,2923cm-1 occur respectively phenyl ring,
Borate absorption peak illustrates that carboxyl react transformation for target product with amino.
Embodiment 9
It is 0.3dL/g by 50g inherent viscosities, the low-molecular-weight liquid carboxyl nitroso that carboxyl mole percent is 1.5% contains
Fluoropolymer（Structure is such as（III）It is shown）Directly with 3- hydroxyl phenyl boric acids（Structure is such as（IV）It is shown）2.45 reaction（That is 3- hydroxyls
The molar ratio of phenyl boric acid and carboxyl nitroso fluoropolymer carboxyl is 1.05:1）, reaction 2h knots at a temperature of stirring, 60 DEG C
Shu Fanying obtains light yellow liquid fluorinated polymer product.The progress for the benefit of reacted can carry out vacuum and extract dehydration in reaction
Processing.Infrared analysis is shown：Wave number carboxyl vibration absorption peak at 1712cm-1 disappears, and ester linkage group suction occurs in 1740cm-1
Peak is received, occurs phenyl ring, borate absorption peak respectively in 1601cm-1,2858cm-1,2930cm-1, illustrates that carboxyl is carried out with hydroxyl
Reaction transformation is for target product.
Embodiment 10
The solid forms high molecular weight carboxyl nitroso fluoropolymer described in embodiment 1- embodiments 5 is prepared, is used
Solution polymerization process described in patent CN102731784B, specific preparation process can be used the mode of embodiment 1 but not only limit
In embodiment 1.
It is evacuated after polymeric kettle is replaced with nitrogen, -65 DEG C of ethyl alcohol cycle cold mediums is passed through in chuck, polymeric kettle is cold
To -30 DEG C, using the vacuum state of polymeric kettle, Trifluoronitrosomethane and Nitrosoperfluorobutyric acid 100g, dichloromethane are sequentially added with suction
4.6kg.Polymerization kettle agitator is opened, continues to be passed through -65 DEG C of ethyl alcohol cycle cold mediums in chuck, until polymerization kettle temperature reaches -45 DEG C
When, nitroso fluoroform 3.0kg is added, this material liquefies in kettle and heat release can cause kettle temperature to be increased.Due to following
Ring cold medium declines once more in continuous refrigeration, kettle temperature, and tetrafluoroethene 3.1kg is added when reactor temperature is down to -55 DEG C；
After the completion of charging, polymeric kettle is allowed to heat up naturally, after temperature in the kettle rises to -45 DEG C, binary polymerization reaction starts simultaneously
Release heat.Holding is passed through cycle cold medium, and by the control of reaction kettle Inner temperature at -35 DEG C, initial pressure 0.6MPa is small through 20
Shi Hou, pressure are down to 0.25MPa, stop stirring and are passed through cycle cold medium, replace kettle Inner residual air 3 times with nitrogen, work as reaction kettle
Temperature when being warmed to room temperature naturally, open polymerization kettle bottom valve and release dichloromethane, carboxyl nitroso fluorine is taken out from polymeric kettle top
Rubber, to get CNR raw rubbers after water washing, dehydration, except postprocessing working procedures such as low molecules（That is carboxyl nitroso fluoropolymer）
5.55kg。
0.55 dL/g of inherent viscosity of the raw rubber, acid content 0.62%（mol）, yield 89.9%.
Embodiment 11
The liquid form low molecular weight carboxyl nitroso fluoropolymer described in embodiment 6- embodiments 9 is prepared, is used
Solution polymerization process described in patent CN103214613B, specific preparation process can be used the mode of embodiment 3 but not only limit
In embodiment 3：
It is evacuated after stainless steel polymeric kettle is replaced with nitrogen, the ethyl alcohol of -70 DEG C of cold medium of cycle is led in chuck, it will be empty
Kettle is cooled to -60 DEG C；Using the vacuum state of polymeric kettle, γ-Trifluoronitrosomethane and Nitrosoperfluorobutyric acid 100g, molecule are sequentially added with suction
3.5 liters of chain-transferring agent ether 175g, dichloromethane；Nitroso fluoroform is added in gas phase under less than -45 DEG C states of kettle temperature control
Alkane 1.95kg；Tetrafluoroethene 2.38kg is added in gas phase under the conditions of kettle temperature is less than -50 DEG C.
Polymerisation opens kettle liquid separation and extracts methylene chloride and liquid polymer out respectively after 18 hours.Polymer passes through
Water washing, dehydration after removing the postprocessing working procedures such as low molecule, obtain being in yellowish transparency liquid raw rubber（That is carboxyl nitroso contains
Fluoropolymer）2.48kg, after tested, inherent viscosity 0.06/dLg-1, acid content 1.36%（mol）, dynamic viscosity is
61Pa.s。
The cross moulding of 12 polymer of embodiment
With the fluoropolymer 30g prepared by embodiment 2, mixed on a mill with fume colloidal silica R812S 8g
Even mixing, compounded compositions are in blocks according to condition 15MPa × 70 DEG C × 1h hot pressing on vulcanizing press, test it and stretch by force
Degree, elongation at break are respectively 5.3MPa, 320%.Prepared print is impregnated in normal-temperature water, is in that solution is handed over completely after 72h
Connection state.It is still in blocks according to condition 15MPa × 70 DEG C × 1h hot pressing after the composition is carried out dehydrating, test its stretching
Intensity, elongation at break are respectively 5.1MPa, 280%.Illustrate that the composition realizes friendship by side chain phenyl boric acid to borine transformation
It is unified into type, borine can then solve crosslinking under hydrone effect and be changed into boric acid, and boric acid is changed into borine and can realize again again to be cross-linked into
Type.
The cross moulding of 13 polymer of embodiment
It is replaced with the fluoropolymer 30g prepared by embodiment 4, other operations are the same as embodiment 12.Test shows it
Tensile strength, elongation at break are respectively 5.5MPa, 310%.Prepared composition print is impregnated in 50 DEG C of water, by for 24 hours
Afterwards i.e. in solution cross-linked state completely.After the composition is carried out dehydrating, still it is hot pressed into according to condition 15MPa × 70 DEG C × 1h
Piece tests its tensile strength, elongation at break is respectively 5.2MPa, 280%.Also illustrate the composition by side chain phenyl boric acid to
Borine transformation realizes cross moulding, and borine then solves crosslinking transformation for boric acid under hydrone effect, and boric acid is changed into boron again
Alkane can realize molding crosslinking again.
The cross moulding of 14 polymer of embodiment
Fluoropolymer solutions prepared by Example 3 are evenly applied to glass plate, and solvent carries out nature volatilization, solvent
Fully prepared test plate is placed in together in 60~70 DEG C of convection ovens after volatilization and carries out heat treatment 8h, glass plate is taken off
Uniform transparent elastic composition film is obtained after removing.Composition film is impregnated in room temperature water, is sent out by rear film for 24 hours
Raw solution crosslinking.By polymer taking-up heat in 60~70 DEG C of convection ovens again, after 8h again cross moulding
For elastomer.Illustrate that boric acid-borine conversion cross moulding also has occurred in polymer, borine has occurred to boric acid again under water effect
Transformation.
The measurement that embodiment 15 is used as adhesive is tested
With the fluoropolymer prepared by embodiment 7, carried out according to adhesive tensile shear strength standard GB7124-2008
Aluminium alloy bonds, and bonds aluminum alloy specimen and is heat-treated 8h in 60~70 DEG C of convection ovens, measures its shearing peel strength and is
2.8MPa。
Claims (9)
1. a kind of fluoropolymer, it is characterised in that：With as follows（I）Shown in molecular structure：
Wherein R represents the alkyl of H or C1~C5；X represents amide or ester bond valence bond structure unit；Main polymer chain is nitrous
The repetitive unit of base-tetrafluoroethene, side chain couple phenyl boric acid unit by amide or ester bond valence link；M and n represent the degree of polymerization.
2. a kind of fluoropolymer according to claim 1, it is characterised in that：It is described（I）Shown molecular structure it is fluorine-containing
Polymer be by（III）The carboxyl nitroso fluoropolymer of shown structure with（IV）The phenyl boric acid of shown structure, passes through（II）
It is prepared by the shown reaction mechanism mechanism of reaction：
Wherein（III）The carboxyl nitroso fluoropolymer of shown structure carries carboxyl-reactive structural unit,（IV）Shown structure
Phenyl boric acid carry amino or hydroxyl reaction active group.
3. a kind of fluoropolymer according to claim 2, it is characterised in that：It is described（III）The carboxyl of shown structure is sub-
Nitro fluoropolymer is the terpolymer of nitroso fluoroform, tetrafluoroethene and γ-Trifluoronitrosomethane and Nitrosoperfluorobutyric acid, the polymerization
Object carboxyl mole percent is 0.5~1.5%.
4. a kind of fluoropolymer according to claim 2, it is characterised in that：It is described（IV）The phenyl boric acid of shown structure selects
From one or any two or more in 3- amino phenyl boric acid, 4- amino phenyl boric acid, 3- hydroxyls phenyl boric acid, 4- hydroxyl phenyl boric acids
Combination.
5. a kind of fluoropolymer cross-linking agent, it is characterised in that：It is by will be described in claim 1（I）Shown molecular structure
Fluoropolymer-containing side chain phenyl boric acid changes crosslinking to borine and is formed, and the borine of the cross-linking agent solves crosslinking under hydrone effect
It is changed into boric acid, phenyl boric acid is converted to borine and realizes cross moulding again again.
6. a kind of fluoropolymer-containing preparation method described in claim 1, it is characterised in that：It is described（I）Shown molecular structure
Fluoropolymer be take bulk process or solution methods to carry out reaction preparation.
7. a kind of fluoropolymer-containing preparation method described in claim 2, it is characterised in that：Reaction system is carried out with solution methods
When standby, concrete operation step is as follows：First will（III）The carboxyl nitroso fluoropolymer of shown structure is dissolved in three chloroethene of trifluoro
Alkane or perfluoroparaffin are formulated as solution, are then added again into solution（IV）The phenyl boric acid of shown structure, in stirring, 50~80 DEG C of temperature
2~5h of the lower reaction of degree is obtained（I）The fluoropolymer product of shown molecular structure；
It is described（III）The carboxyl nitroso fluoropolymer of shown structure is formulated as a concentration of 5~30wt% of solution；
It is described（IV）The phenyl boric acid of shown structure with（III）The molar ratio of the carboxyl nitroso fluoropolymer carboxyl of shown structure
Example is 1.05~1:1.
8. a kind of fluoropolymer-containing preparation method described in claim 2, it is characterised in that：It is prepared with bulk process
When, concrete operation step is as follows：It will（III）The low-molecular-weight liquid carboxyl nitroso fluoropolymer of shown structure is directly same
（IV）The phenyl boric acid of shown structure carries out bulk reaction and is prepared（I）The fluoropolymer product of shown molecular structure；It is described
（IV）The phenyl boric acid of shown structure with（III）The molar ratio of the carboxyl nitroso fluoropolymer carboxyl of shown structure is 1.05
~1:1, the reaction time is 2~5h, and reaction temperature is controlled at 50~80 DEG C；
The fluoropolymer-containing inherent viscosity ＜ 0.3dL/g of low-molecular-weight liquid carboxyl nitroso, carboxyl-content >=
0.5mol%。
9. a kind of application of fluoropolymer as described in claim 1 as adhesive or sealing material.
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| US3427279A (en) * | 1966-06-14 | 1969-02-11 | Thiokol Chemical Corp | Nitrogen tetroxide resistant carboxy-nitroso terpolymer |
| US3759868A (en) * | 1970-12-28 | 1973-09-18 | Trw Inc | Carboxynitroso polybutadiene vulcanizate |
| JP3115175B2 (en) * | 1993-12-21 | 2000-12-04 | 住友精化株式会社 | Detoxification of high-order borane |
| CN102731784B (en) * | 2012-07-18 | 2013-12-11 | 中蓝晨光化工研究设计院有限公司 | Carboxyl nitroso-fluoro rubber (CNR) solution polymerization process |
| CN103214613B (en) * | 2013-04-17 | 2015-08-26 | 中蓝晨光化工研究设计院有限公司 | A kind of nitroso-fluoro-elastomers solution polymerization process |
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