CN101717464A - Preparation method of carboxyl-terminated liquid fluorine polymer - Google Patents
Preparation method of carboxyl-terminated liquid fluorine polymer Download PDFInfo
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- CN101717464A CN101717464A CN200910236784A CN200910236784A CN101717464A CN 101717464 A CN101717464 A CN 101717464A CN 200910236784 A CN200910236784 A CN 200910236784A CN 200910236784 A CN200910236784 A CN 200910236784A CN 101717464 A CN101717464 A CN 101717464A
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Abstract
The invention discloses a preparation method of a carboxyl-terminated liquid fluorine polymer, comprising the following steps of: dissolving a solid fluorine elastomer in an organic solvent, adding oxidant and alkali, and stirring to react for 5 to 20 hours, wherein the reaction temperature is controlled within 10 to 70 DEG C, and the reaction pressure is self-generated pressure of a system; standing for 8 to 12 hours after reaction stops, and then recovering the carboxyl-terminated liquid fluorine polymer. The preparation method has the advantages of simple and easy process, less side reactions, high production ratio and low cost. The invention also discloses a solidification method of the carboxyl-terminated liquid fluorine polymer, and the carboxyl-terminated liquid fluorine polymer is reacted with an organic compound containing two or more than two epoxide groups or polyvalent metal oxides and solidified.
Description
Technical field
The present invention relates to a kind of preparation and curing of carboxyl-terminated liquid fluorine polymer.
Background technology
Carboxyl-terminated liquid fluorine polymer has excellent thermotolerance, oxidation-resistance and chemical resistance, can be solidified into the shape of any needs as required at a lower temperature, being specially adapted to the sealing of cohering under the severe condition, top layer protection and hole, is the ideal aircraft industry with sealing material, tackiness agent and coating.
At present, carboxyl-terminated liquid fluorine polymer mainly is to prepare by add suitable molecular weight regulator in the polymerization system of fluoroelastomer, and this method building-up process complexity is loaded down with trivial details, and side reaction and intermediate product are more, and productive rate is lower, and cost is higher.
US patent 3; 438; 953 disclose a kind of method of the liquid fluorine polymkeric substance with vinylidene, R 1216 comonomer and superoxide (two-(ω-carboxyl ester perfluoro acidyl)) prepared in reaction carboxyl-ester terminated; promptly under temperature is lower than 10 ℃ condition, peroxide aqueous solution is joined in the liquid fluorocarbon mixture that is dissolved with perfluor dicarboxylic acid acyl chlorides monoesters; vigorous stirring makes system generate the peroxidation diacyl; then fluorine carbon and residual water are separated, to fluorine carbon add in mutually vinylidene and R 1216 in autogenous pressure down reaction make.The raw material of using in this method is two-and (ω-carboxyl ester perfluoro acidyl) be that the perfluor diacid chloride is generated in-situ in polymerization process; and reaction back liquid fluorine polymkeric substance need be separated by distillation and unreacted diacid chloride and diester; reaction yield is greatly about about 50%; so this procedure complexity; side reaction is more, and productive rate is lower.In addition, the polymkeric substance that this method makes mostly is ester terminated, also will be with the hydrolysis in warm water of ester terminated polymkeric substance if will make the polymkeric substance of carboxy blocking.
US patent 4,361,678 discloses a kind of method of passing through emulsion polymerization prepared liquid fluorine polymkeric substance with vinylidene and at least a fluoroolefin under the condition that iodide exist.A little less than this method utilizes the C-I key, thus the principle that in the presence of radical initiator, ruptures and carry out addition reaction easily.The massfraction of terminal iodine is between 1%～30% in the liquid fluorine polymkeric substance that this method makes, and this terminal iodine is comparatively active, can be converted into carboxyl, but this preparation method's productive rate is very low.
The chain propagation agent that carboxyl-terminated liquid fluorine polymer can be used as Resins, epoxy uses, and also can be used as raw material and is used for preparing sealing agent, tackiness agent etc.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of carboxyl-terminated liquid fluorine polymer, it has the advantages that process is simple, side reaction is few, productive rate is high and cost is low.Another object of the present invention provides the curing of this carboxyl-terminated liquid fluorine polymer.
The present invention is by being dissolved in the solid fluoroelastomer in the organic solvent and adding alkali and oxygenant makes it that oxidative degradation take place to make carboxyl-terminated liquid fluorine polymer.May further comprise the steps:
(a) the solid fluoroelastomer was dissolved in organic solvent 12～24 hours, can powerfully stir with accelerate dissolution.The characteristics of this solid fluoroelastomer are as follows: the molar fraction of vinylidene is between 30～80%, and weight-average molecular weight is 5～9.5 * 10
5Between, number-average molecular weight is 2～6 * 10
5Between, the limiting viscosity of the anhydrous propanone solution of mass concentration 0.1% is 0.15～0.30 in the time of 30 ℃.
(b) add oxygenant and alkali, stir reaction down 5～20 hours, the temperature of reaction is controlled between 10～70 ℃, and the pressure of reaction is the autogenous pressure of system.The addition sequence of alkali and oxygenant is to add alkali earlier to add oxygenant again, or adds simultaneously.Disposable adding of alkali and oxygenant or adding in batches.The consumption of alkali can directly influence the carboxyl-content in the carboxyl-terminated liquid fluorine polymer, and its consumption is to add 0.1～0.7mol for suitable in every 100g solid fluoroelastomer.The amount of substance of oxygenant is 0.5～2.0 times of amount of alkaloid substance.
(c) system left standstill 8～12 hours behind the stopped reaction, reclaimed carboxyl-terminated liquid fluorine polymer then, by the organic phase in the reaction system is realized with the deionized water elution.For removing the impurity in the product, dried product can be dissolved in the organic solvent, treat to dissolve fully back deionized water elution, get final product for 3～4 times repeatedly, in vacuum drying oven, be dried to constant weight then, promptly obtain carboxyl-terminated liquid fluorine polymer, this polymkeric substance is the oily viscous liquid, 60 ℃ of current downflow are better, and the thickness that becomes under the room temperature presents semi-solid state.The limiting viscosity of mass concentration 0.3% anhydrous propanone solution is 0.004～0.02 in the time of 30 ℃, and carboxyl-content is 0.5%～3.0%, and number-average molecular weight is 3 * 10
3～8 * 10
3Between.
The solid fluoroelastomer that the present invention uses can be vinylidene and following any or two kinds of monomeric multipolymers: tetrafluoroethylene, five fluorine propylene, R 1216, a chlorotrifluoroethylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, ethene, propylene etc.Specifically, the multipolymer of the present invention's use can be vinylidene-TFE copolymer, vinylidene-a chlorotrifluoroethylcopolymer copolymer, vinylidene-perfluoro methyl vinyl ether multipolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-perfluoroethylvinyl ether multipolymer, biasfluoroethylene-hexafluoropropylene-tetrafluoroethylene terpolymer, vinylidene-propylene-tetrafluoroethylene terpolymer, vinylidene-tetrafluoroethylene-perfluoroethylvinyl ether terpolymer etc.The solid fluoroelastomer that the present invention uses also can be the waste material of sulfuration viton, as: small pieces, sizing material of making sad work of it etc., need to prove, this class viton waste material also need be the vinylidene and the multipolymer of other a kind of Fluorine containing olefines at least, and this class viton adopts amine, polyvalent alcohol or peroxide cure moulding more usually.
The solvent that the used organic solvent of dissolved solids fluoroelastomer almost can select for use all can dissolve the vinylidene analog copolymer among the present invention, as: acetone, methylethylketone, tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE, ester class, low fatty acid, halogen contained compound (trifluoroacetic acid, hexafluoroisopropanol) etc.
Employed alkali can be tertiary amine, three grades of phosphorus among the present invention, as: triethylamine, trialkyl phosphorus etc.; Also can be the oxyhydroxide or the carbonate of basic metal or alkaline-earth metal, as: sodium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide etc.
Oxygenant used in the present invention mostly is superoxide, can be persulphate, peracetic acid, hydrogen peroxide, organo-peroxide, organic hydroperoxide etc.
In reaction process, fully dissolve in order to make high molecular solid fluoroelastomer, improve speed of reaction and productive rate, recommend to use a kind of phase-transfer catalyst, be a kind of tetravalence complex cation alite usually, as tetravalence ammonium salt or tetravalence microcosmic salt.
The general structure of tetravalence ammonium salt or tetravalence microcosmic salt is as follows:
(R
1R
2R
3R
4N)
+X
-
(R
1R
2R
3R
4P)
+X
-
R wherein
1Arrive
R4 are respectively any in alkyl, alkoxyl group, aryl, aralkyl or the polyoxyethylene groups of 1～25 carbon atom; X
-Be negative ion, as: Cl
-, Br
-, I
-, H
2PO
4 -, RCOO
-, CO
3 2-Deng.Specifically, the tetravalence ammonium salt can be: tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Trimethyllaurylammonium bromide, hexadecyldimethyl benzyl ammonium ethyl ammonium chloride, octadecyl trimethylammonium bromide, benzyltriethylammoinium chloride, benzyl trimethyl ammonium borate, pyrisept, cetyl pyridinium bromide, cetyl pyridinium iodide, cetyl pyridinium vitriol, tetraethyl-ammonium acetate etc.; The tetravalence microcosmic salt can be: tetraphenylphosphonichloride chloride phosphorus, Tetrakis hydroxymethyl phosphonium chloride, four octyl group phosphorus chloride, BPP, benzyl tri-phenyl-phosphorus bromide, benzyl trioctylphosphine phosphorus chloride, trioctylphosphine methyl bromo-phosphonium, trioctylphosphine ethyl acetic acid phosphorus, hexadecyldimethyl benzyl ammonium benzyl phosphorus chloride etc.
Carboxyl-terminated liquid fluorine polymer among the present invention is by solidifying with the organic compound reaction that contains two or more epoxide groups.Suitable epoxy compounds comprises glycidyl ether type, glycidyl ester type, glycidic amine type, acrylic type etc.Specifically can adopt: vinyl cyclohexene diepoxide, many hydrogen aromatic compound glycidyl ether, divinyl diepoxide, Dicyclopentadiene (DCPD) diepoxide, Bisphenol F glycidyl ether etc.Mass ratio when carboxyl-terminated liquid fluorine polymer mixes with epoxy compounds is generally 100: 20～30, different slightly different according to epoxy equivalent (weight).Carboxyl-terminated liquid fluorine polymer among the present invention can also react by the oxide compound with polyvalent metal and solidify, as: magnesium oxide etc.Mass ratio when carboxyl-terminated liquid fluorine polymer mixes with polyvalent metal oxides is generally 100: 5～15.Concrete solidification process is: carboxyl-terminated liquid fluorine polymer heats 30min down at 60 ℃, and is on three-roll grinder that carboxyl-terminated liquid fluorine polymer and stoichiometric solidifying agent thorough mixing is even, then in die for molding.Curing can be carried out in the temperature range of room temperature to 150 ℃, under the room temperature reaction slow, needed several days or the longer time just can completion of cure, then only need several hrs if solidify down at 80～150 ℃.
The preparation method who relates among the present invention, process is simple, with low cost, productive rate is more than 85%, do not need harsh pollution control measures, the carboxyl-terminated liquid fluorine polymer that obtains can be used as the chain propagation agent of Resins, epoxy, also can be used as feedstock production sealing agent, tackiness agent etc., can not add solvent in the preparation process or add a small amount of solvent.This carboxyl-terminated liquid fluorine polymer can be used for sealing, loading erose slit, hole, and this is that the solid fluoroelastomer is not allowed facile.
Embodiment
Embodiment 1
(mol ratio is 80/20, number-average molecular weight Mn=5.2 * 10 with the 5g vinylidene fluoride-hexafluoropropylene copolymer
4, weight-average molecular weight Mw=9.0 * 10
5, the limiting viscosity [η]=0.15 of the anhydrous propanone solution of mass concentration 0.1% in the time of 30 ℃) and in 60g acetone, dissolve 12h.Take by weighing the superoxol 1.3g of mass concentration 30%, potassium hydroxide 0.5g also is dissolved in the 4ml water, and superoxol and potassium hydroxide solution are joined in the system with the speed of 1 of per second simultaneously, and the system color changes.Keep system temperature at 64 ℃, stir reaction 5h down, leave standstill 8h then.
Supernatant liquid in the reaction mixture is toppled over,, till as clear as crystal, the no oily small droplets of washings suspends, thereby obtain product with 4 times of deionized water wash organic phases to the organic phase volume.And then product is dissolved in the acetone dissolving back deionized water wash, this step 3 times repeatedly fully.In 60 ℃ of vacuum drying ovens, remove residual solvent then, be dried to constant weight.
Obtain the water white viscous liquid of 4.3g (ρ (50 ℃) is 161Pas), 60 ℃ of current downflow are good, and the thickness that becomes under the room temperature presents semi-solid state, and the limiting viscosity of the anhydrous propanone solution of mass concentration 0.3% is 0.018 in the time of 30 ℃.Infrared analysis shows that product is at 1770cm
-1There is strong absorption peak at the place, and showing has-CF
2The existence of COOH group.The neutralization equivalent of product is 4414, and carboxyl-content is 1.02%.
Embodiment 2
(mol ratio is 65/15/20, number-average molecular weight Mn=5.8 * 10 with 20g biasfluoroethylene-hexafluoropropylene-TFE copolymer
4, weight-average molecular weight Mw=9.4 * 10
5, the limiting viscosity [η]=0.157 of the anhydrous propanone solution of mass concentration 0.1% in the time of 30 ℃) and in the 160g tetrahydrofuran (THF), dissolve 24h.1.1g potassium hydroxide is dissolved in the 8ml water, adds in the reaction system, the system color changes.The superoxol that then adds the mass concentration 30% of 5.7g, adding speed are 1 of p.s..Keep system temperature at 54 ℃, stir reaction 15h down, leave standstill 12h then.
The aftertreatment of reaction system and washing process are with embodiment 1.
Obtain the faint yellow viscous liquid of 17.6g (ρ (50 ℃) is 150Pas), the limiting viscosity of 0.3% anhydrous propanone solution is 0.017 in the time of 30 ℃.Infrared analysis shows, product is that the molecular chain two ends have-fluorine-containing oligomer (1760cm of COOH
-1C=O).The neutralization equivalent of product is 4150, and carboxyl-content is 1.08%.
Embodiment 3
(physical parameter is with embodiment 1) is dissolved in the 60g acetone with the 5g vinylidene fluoride-hexafluoropropylene copolymer, dissolving 12h.Take by weighing benzyltriethylammoinium chloride 0.1g, add in the reaction system, stir reaction 20min down.Take by weighing the 0.4g triethylamine, with p.s. 1 speed join in the reaction system, stir reaction 1h down.Superoxol with 0.4g triethylamine and 1.7g mass concentration 30% joins in the system simultaneously then.54 ℃ of following stirring reaction 12h, stopped reaction, reaction system leaves standstill 12h.
Pour out the aqueous phase layer in the reaction mixture, till residual organic phase suspends with deionized water wash to the transparent no oily small droplets of washings.Promptly obtain the product of wanting after the drying, and then product is dissolved in the acetone, fully dissolving back deionized water wash, this step 4 times repeatedly.Final product is the faint yellow viscous liquid of 4.6g, and the feature of this product is as follows:
Dynamic viscosity: 94Pas (50 ℃)
Limiting viscosity: the 0.011 anhydrous propanone solution of mass concentration 0.3% (30 ℃ time)
Number-average molecular weight: Mn=5000 (is the GPC test result of standard specimen with the polystyrene)
Infrared absorption peak: 1766cm
-1C=O
1H-NMR (SiMe
4Be interior mark): 7.50～7.70ppm-COOH
Embodiment 4
In embodiment 3, do not use benzyltriethylammoinium chloride, stopped reaction behind the reaction 7h under stirring.
Obtain the faint yellow viscous liquid of 4.25g, dynamic viscosity 89Pas, the limiting viscosity of the anhydrous propanone solution of mass concentration 0.3% is 0.010 in the time of 30 ℃.
Embodiment 5
Form with 17% mass percent acetone soln in the 3.0L there-necked flask (being furnished with agitator, dropping funnel and thermometer respectively) adds the 100g vinylidene fluoride-hexafluoropropylene copolymer, take by weighing the 5.0g BPP, add in the reaction system, stir reaction 30min down, add 19.6g potassium hydroxide then, system is in 64 ℃ of following reflux 30min.Then, add 19.6g potassium hydroxide again and stir reaction 30min down.Take by weighing the 30.0g Sodium Persulfate and be dissolved in the 180ml deionized water, be divided in the two equal portions adding systems, the timed interval of twice adding is 20min.System stops after under agitation reacting 20h, leaves standstill 12h.
The aftertreatment of reaction system and washing process are with embodiment 1.
Obtain the faint yellow viscous liquid of 97.0g, the dynamic viscosity ρ in the time of 50 ℃ is 72Pas, and the limiting viscosity of the anhydrous propanone solution of mass concentration 0.3% is 0.007 in the time of 30 ℃.Infrared and nmr analysis shows that product is the fluorine-containing oligomer that has carboxyl.Number-average molecular weight Mn is 4500, and neutralization equivalent is 2323, and carboxyl-content is 1.94%.
Embodiment 6～11
Specific implementation method is with embodiment 1, and just the consumption and the temperature of reaction of the hydrogen peroxide of mass concentration 30% change to some extent, specifically changes as shown in table 1ly, and the gained result also lists in table 1.Wherein: IR represents is in the infrared spectra-CF
2The position of COOH characteristic peak; What ρ (50 ℃) represented is the dynamic viscosity of 50 ℃ of following polymkeric substance; Mn represents is number-average molecular weight by the polymkeric substance of GPC test;-COOH represents is carboxyl-content in the polymkeric substance, is recorded by titration method.
| ??H 2O 2??(g) | Temperature of reaction (℃) | Productive rate (%) | ??IR??(cm -1) | ??ρ(50℃)??(Pa·s) | ??Mn | ??-COOH??(％) | |
| Embodiment 6 | ??1.0 | ??10 | ??79 | ??1761 | ??166 | ??8100 | ??0.86 |
| Embodiment 7 | ??2.0 | ??54 | ??90 | ??1768 | ??157 | ??7000 | ??1.09 |
| Embodiment 8 | ??2.5 | ??70 | ??89 | ??1768 | ??148 | ??6300 | ??1.27 |
| Embodiment 9 | ??1.3 | ??24 | ??97 | ??1771 | ??75 | ??4500 | ??2.16 |
| Embodiment 10 | ??1.3 | ??34 | ??95 | ??1763 | ??80 | ??4600 | ??1.94 |
| Embodiment 11 | ??1.3 | ??44 | ??85 | ??1765 | ??87 | ??4800 | ??1.87 |
Embodiment 12
With the heating 30min under 60 ℃ of synthetic carboxyl-terminated liquid fluorine polymer among 100 parts of embodiment 1, sneak into 30 parts Resins, epoxy E-42 (epoxy equivalent (weight) 266), on three-roll grinder, mix, put into mould.Condition of cure is: 80 ℃/5h+120 ℃/3h+150 ℃/40min, cured article is a kind of faint yellow solid, soaks 3 days in solvent under the room temperature, and the result is as shown in table 2.
| Solvent | Quality increases (%) |
| Acetone | ??2.1 |
| Hexanaphthene | ??0.7 |
| Toluene | ??6.7 |
Embodiment 13～15
In embodiment 11, adopt different Resins, epoxy and consumption, different conditions of cure, the product after the curing at room temperature soaked 3 days in different solvents, surveyed the percentage ratio that its quality increases, and the gained result is as shown in table 2.Wherein, the epoxy equivalent (weight) of Resins, epoxy E-51 is 190.
| Resins, epoxy (consumption, part) | Condition of cure | Acetone | Hexanaphthene | |
| Embodiment 13 | ??E-51(20) | ??80℃/5h+120℃/5h+150℃/1h | ??3.0 | ??0.9 |
| Embodiment 14 | ??E-51(25) | 130 ℃/1h+ room temperature/27d | ??4.2 | ??1.2 |
| Embodiment 15 | ??E-42(27) | 80 ℃/2h+ room temperature/21d | ??5.0 | ??1.7 |
Embodiment 16
With the heating 30min under 60 ℃ of synthetic carboxyl-terminated liquid fluorine polymer among 100 parts of embodiment 4, add 8g magnesium oxide, after mixing, at room temperature place 30min, move in the mould, curing 10h obtains Hookean body under 100 ℃.Soaked 3 days in No. 3 oil of ASTM under this solid room temperature, quality increases by 0.7%.
Embodiment 17～19
In embodiment 16, change magnesian consumption, obtaining the quality that cured product soaks in No. 3 oil of ASTM after 3 days increases as shown in table 3.
| Magnesium oxide consumption (part) | Quality increases (%) | |
| Embodiment 17 | ??5 | ??1.2 |
| Embodiment 18 | ??11 | ??0.6 |
| Embodiment 19 | ??15 | ??0.8 |
Claims (10)
1. the preparation method of a carboxyl-terminated liquid fluorine polymer is characterized in that, makes by solid fluoroelastomer and alkali and oxygenant generation oxidative degradation, may further comprise the steps:
(a) the solid fluoroelastomer was dissolved in organic solvent 12～24 hours, can powerfully stir with accelerate dissolution.The characteristics of this solid fluoroelastomer are as follows: the molar fraction of vinylidene is between 30～80%, and weight-average molecular weight is 5～9.5 * 10
5Between, number-average molecular weight is 2～6 * 10
5Between, the limiting viscosity of the anhydrous propanone solution of mass concentration 0.1% is 0.15～0.30 in the time of 30 ℃.
(b) add oxygenant and alkali, stir reaction down 5～20 hours, the temperature of reaction is controlled between 10～70 ℃, and the pressure of reaction is the autogenous pressure of system.The addition sequence of alkali and oxygenant is to add alkali earlier to add oxygenant again, or add simultaneously, disposable adding of alkali and oxygenant or adding in batches, the consumption of alkali can directly influence the carboxyl-content in the carboxyl-terminated liquid fluorine polymer, its consumption to be adding 0.1～0.7mol for suitable in every 100g solid fluoroelastomer, the amount of substance of oxygenant is 0.5～2.0 times of amount of alkaloid substance.
(c) system left standstill 8～12 hours behind the stopped reaction, reclaimed carboxyl-terminated liquid fluorine polymer then, by the organic phase in the reaction system is realized with the deionized water elution.For removing the impurity in the product, dried product can be dissolved in the organic solvent, treat to dissolve fully back deionized water elution, get final product for 3～4 times repeatedly, in vacuum drying oven, be dried to constant weight then, promptly obtain carboxyl-terminated liquid fluorine polymer, this polymkeric substance is the oily viscous liquid, 60 ℃ of current downflow are better, and the thickness that becomes under the room temperature presents semi-solid state.The limiting viscosity of mass concentration 0.3% anhydrous propanone solution is 0.004～0.02 in the time of 30 ℃, and carboxyl-content is 0.5%～3.0%, and number-average molecular weight is 3 * 10
3～8 * 10
3Between.
2. according to the preparation method of claim 1, it is characterized in that described solid fluoroelastomer is vinylidene and following any or two kinds of monomeric multipolymers: tetrafluoroethylene, five fluorine propylene, R 1216, a chlorotrifluoroethylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, ethene, propylene.
3. according to the preparation method of claim 1, it is characterized in that described solid fluoroelastomer is the vinylidene and the sulfuration viton of the multipolymer of other a kind of Fluorine containing olefines at least.
4. according to the preparation method of claim 1, it is characterized in that described oxygenant is a superoxide.
5. according to the preparation method of claim 4, it is characterized in that described superoxide is persulphate, peracetic acid, hydrogen peroxide, organo-peroxide, organic hydroperoxide.
6. according to the preparation method of claim 1, it is characterized in that described alkali is the oxyhydroxide or the carbonate of tertiary amine, three grades of phosphorus or basic metal or alkaline-earth metal.
7. according to arbitrary preparation method of claim 1-6, it is characterized in that, in step (a) process, add a kind of phase-transfer catalyst of tetravalence complex cation alite.
8. according to the preparation method of claim 7, it is characterized in that described phase-transfer catalyst is tetravalence ammonium salt or tetravalence microcosmic salt, its general structure is as follows:
(R
1R
2R
3R
4N)
+X
-
(R
1R
2R
3R
4P)
+X
-
Wherein R1 is respectively any in alkyl, alkoxyl group, aryl, aralkyl or the polyoxyethylene groups of 1～25 carbon atom to R4; X
-Be negative ion.
9. according to the curing of the made carboxyl-terminated liquid fluorine polymer of arbitrary preparation method among the claim 1-8, it is characterized in that, carboxyl-terminated liquid fluorine polymer is by solidifying with the organic compound reaction that contains two or more epoxide groups, and the mass ratio when carboxyl-terminated liquid fluorine polymer mixes with epoxy compounds is 100: 20～30.
Concrete solidification process is: carboxyl-terminated liquid fluorine polymer heats 30min down at 60 ℃, and is on three-roll grinder that carboxyl-terminated liquid fluorine polymer and stoichiometric solidifying agent thorough mixing is even, then in die for molding.Be solidificated in the temperature range of room temperature to 150 ℃ and carry out.
10. according to the curing of claim 9, it is characterized in that carboxyl-terminated liquid fluorine polymer is by solidifying with the oxide compound reaction of polyvalent metal, the mass ratio when carboxyl-terminated liquid fluorine polymer mixes with polyvalent metal oxides is 100: 5～15.
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