CN104448097A - Perfluor dioxole-modified fluorine-containing polymer - Google Patents
Perfluor dioxole-modified fluorine-containing polymer Download PDFInfo
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- CN104448097A CN104448097A CN201410667639.5A CN201410667639A CN104448097A CN 104448097 A CN104448097 A CN 104448097A CN 201410667639 A CN201410667639 A CN 201410667639A CN 104448097 A CN104448097 A CN 104448097A
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Abstract
The invention belongs to the field of organic chemistry and relates to a perfluor dioxole-modified fluorine-containing polymer. A general formula of the perfluor dioxole is as shown in the specification, wherein R and F represent RF or ORF; RF is C1-C5 linear or branched perfluoroalkyl; X1 and X2 are independently used as F or CF3; and a fluorine-containing olefin monomer accounts for 80-99.1% of mass of a copolymerized monomer. According to the polymer disclosed by the invention, the glass-transition temperature is greater than 65 DEG C; the particle size is smaller than 120mum; the intrinsic viscosity is greater than 1.0dl/g; the polymer can be completely dissolved into common esters and other strong polar solvents; the problems that the glass-transition temperature of F23 fluorine polymers at present is relatively low and the like are solved; and the polymer can be widely applied to the military industry, and can be used as a binder for a polymer-bonded explosive and a binder for current collector metal for cells.
Description
Technical field
The invention belongs to field of organic polymer compound, be specifically related to a kind of vinylidene fluoride copolymers and preparation method thereof.
Background technology
Fluoropolymer has the many advantageous properties not available for hydrocarbon polymer, has comparatively low surface tension and frictional coefficient, excellent thermotolerance, scale resistance, chemical proofing.Polyvinylidene difluoride (PVDF) trifluorochloroethylene (P (VDF-CTFE)) is the one of fluoropolymer.The P (VDF-CTFE) of low CTFE content has higher dipole density and energy density, and its film formed has the velocity of discharge quickly and lower loss, and this makes the application of P (VDF-CTFE) have more realistic meaning.The P (VDF-CTFE) of high CTFE content is mainly used as the binding agent of the binding agent of polymer bonding explosive and the current collector metal of battery, is widely used in military affairs, national defence, aerospace system industry.
Viton VDF-CTFE (l:l) random copolymers (trade(brand)name F2311) is vinylidene (VDF)-trifluorochloroethylene C (TFE) random copolymers of monomer mole ratio 1:1, its degree of crystallinity is quite low, second-order transition temperature is about 13 DEG C, brittleness temperature-20 ~-40 DEG C, dissolves in the organic solvents such as ketone, aldehyde, vinegar; Fluoro-resin VDF-CTFE (l:3) random copolymers (trade(brand)name F2313) is monomer mole ratio is the vinylidene (VDF) of 1:3 and the random copolymers of trifluorochloroethylene C (TFE), its crystallization velocity is slow, degree of crystallinity is generally 10 ~ 20%, crystalline melt point is at about 95 DEG C, melting range is within the scope of 70 ~ 130 DEG C, and second-order transition temperature is about 30 DEG C.Domestic and international high performance composite adopt copolymerization ratio be the VDF/CTFE random copolymers (trade(brand)name F2314) of 1: 4 as structural adhesive, but second-order transition temperature is not also higher than 50 DEG C, limits its application in pyroprocessing.
Chinese patent CN101186668A describes a kind of preparation method of fluorine-containing rubber used for paint, mainly polymerization single polymerization monomer is that 50 ~ 80% trifluorochloroethylenes and 20 ~ 50% vinylidenes are under organic initiators and fluorine-containing emulsifier effect, carry out letex polymerization, be polymerized polymkeric substance has different size property viscosity and excellent solubility, but second-order transition temperature is less than 50 DEG C, can not meet some special applications of military project.
U.S. Patent Publication No. be 2752331 and China Patent Publication No. be P (VDF-CTFE) multipolymer that 102585077A introduces low CTFE content, although resulting polymers has higher dipole density and energy density, its film formed has the velocity of discharge quickly and lower loss, but its second-order transition temperature is lower, at normal temperatures, ester class and ketone solvability undesirable.
Because second-order transition temperature be high molecular segment from the transition temperature being frozen into motion, and sub-chain motion transfers realization by the singly-bound inward turning of main chain, affects the factor of macromolecular chain flexibility so every, all can have an impact to Tg.Tg is all made to raise as introduced this macromolecular chain factor that is flexible or that increase Intermolecular Forces that weakens of rigid radical or polar group, crosslinked and crystallization; Factor as added softening agent or this increase macromolecular chain flexibility such as solvent, introduction flexible group all makes Tg reduce.Research both domestic and external concentrates on TATB content and accounts for 95%, and binder content accounts on the polymer bonding explosive of 5%.Therefore polymeric binder is one of principal element affecting polymer bonding explosive property on the covered effect of explosive and cohesive action.
Summary of the invention
The object of this invention is to provide a kind of novel fluoropolymers.In the described novel fluoropolymers of preparation, add a certain amount of perfluorodioxole class modified monomer, to make on the main chain of polymkeric substance, with a certain amount of rigid radical, polar group, to enhance Intermolecular Forces, improve Tg performance.
Another object of the present invention is the preparation method of the fluoropolymer proposing described perfluorodioxole modification.
Realizing the object of the invention technical scheme is:
A fluoropolymer for perfluorodioxole modification, the general formula of described perfluorodioxole is:
Wherein R '
frepresent that RF or ORF, described RF are the perfluoroalkyl of the linear of C1-C5 or branching, X
1and X
2be F or CF independently of each other
3;
Described fluoropolymer is that fluorinated olefin monomers is polymerized the multipolymer obtained, and it is two or more that described fluorinated olefin monomers is selected from vinyl fluoride, vinylidene, trifluoro-ethylene, tetrafluoroethylene, trifluorochloroethylene, tetrafluoroethylene, tetrafluoeopropene, five fluorine propylene, R 1216, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether;
Described fluorinated olefin monomers accounts for 80 ~ 99.1% of the monomer mass carrying out copolymerization.
Preferably, described fluorinated olefin monomers is trifluorochloroethylene and vinylidene, and trifluorochloroethylene, vinylidene, perfluorodioxole account for 65 ~ 85%, 5 ~ 25% and 0.1 ~ 20% of the monomer mass carrying out copolymerization.
Perfluorodioxole is preferable over as perfluorodimethyldioxole (PDD), and the quality proportion optimization ratio that this monomer accounts for total comonomer is 0.1 ~ 10%.When monomer whose content is less than 0.1%, little on the impact of the Tg performance of fluoropolymer; If when monomer content is greater than 10%, although the second-order transition temperature of polymkeric substance is greatly improved, degree of crystallinity is also greatly affected, but its main chain exists the ring-type segment of a large amount of repeating units, its solvability is difficult to dissolve in simple solvent, when as explosive adhesive, in ester, ketone, solvability is poor, TATB (1,3,5-triamino-2,4,6-trinitrobenzene) skewness in fluorine random copolymers, locally there is obvious particle agglomeration phenomenon, be difficult to form uniform film.
Perfluorodimethyldioxole (PDD), can carry out pre-micro emulsion with emulsifying agent and deionized water, make it follow emulsifying agent to be evenly dispersed in deionized water, form microemulsion.Described microemulsion refers under mild stirring effect, and when not providing energy dispersive, perfluorodioxole class modified monomer dissolves in the system obtaining liquid and stable a single phase soln in fluorinated surfactant solution.
The method of the fluoropolymer that preparation the present invention proposes, comprises step:
(1) in reactor, add water, fluorine-containing emulsifier, described water accounts for the 40-70% of reactor volume,
(2) in reactor, add perfluorodioxole class monomer and fluorinated olefin monomers, make reactor reach the pressure of polyreaction; In reactor, add PH conditioning agent, chain-transfer agent, initiator and reductive agent, at 30 DEG C ~ 100 DEG C temperature and 1.0 ~ 6.0MPa pressure, carry out polyreaction;
(3) segmentation or add perfluorodioxole class monomer and fluorinated olefin monomers constantly in reactor, maintenance polymerization pressure is 1.0 ~ 6.0MPa, and the solid content reacting liquid phase to reactor is 25-35%, obtains polymerized emulsion;
(4) polymerized emulsion is carried out freeze agglomeration, washs, dry, pulverize, packs.
Wherein, described fluorine-containing emulsifier is Perfluorocaprylic Acid dipersant, is selected from one or more in Sodium perfluorooctanoate, ammonium perfluorocaprylate or Potassium perfluorooctanoate, and the amount of described fluorine-containing emulsifier is containing 0.001 ~ 4 weight part in every 100 weight parts waters;
As an optimal technical scheme of the present invention, all right adding liquid paraffin or hydrocarbon ils in water, the saturated chloroflo of any long-chain or oil can prevent attachment of polymers on reactor parts, play antifouling effect, and the amount of paraffin or hydrocarbon ils is about 5mg/cm
2reactor internal surface area.Conveniently technique means, can add according to 1 ~ 5% of volume of water.
Wherein, described pH adjusting agent pH adjusting agent of the present invention is the one in dipotassium hydrogen phosphate, Sodium phosphate dibasic, sodium acetate, borax and sodium bicarbonate.PH adjusting agent add-on can add according to 0.03 ~ 0.1 weight part in 100 parts of water.
Wherein, described chain-transfer agent is one or more in ethanol, acetone, chloroform, ethyl acetate, diethyl malonate, and the amount of described chain-transfer agent is containing 0.05 ~ 5 weight part in every 100 weight parts waters.
Wherein, described initiator is one or more in ammonium persulphate, Potassium Persulphate, potassium permanganate, peroxysuccinic acid, cumene peroxide, dialkyl group peroxycarbonates, and the amount of described initiator is containing 0.01 ~ 6 weight part in every 100 weight parts water media
Wherein, described reductive agent is one or more in S-WAT, Sodium Metabisulfite, oxalic acid, iron protochloride, clorox, and the amount of described reductive agent is containing 0.01 ~ 6 weight part in every 100 weight parts water media.
Preferably, described polymerization reactor control carries out at 30 DEG C ~ 80 DEG C temperature and 2.0 ~ 3.5MPa pressure.
Polymeric reaction temperature is 30 ~ 80 DEG C, if temperature is lower than 30 DEG C, uses initiator of the present invention, copolymerization speed is too slow or cannot initiation reaction, but temperature is higher than 80 DEG C, the efficiency of initiation of initiator can be improved, but trifluorochloroethylene easily liquefies, and resulting polymers textural defect high (macromolecular chain vinylidene and trifluorochloroethylene distribution irregularity, branching, microgel), be difficult to during polyreaction maintain emulsion intercalation method, also may there is the block that hardens, hinder speed of reaction; Gained multipolymer is in the ester class of polarity, and the solvability of ketone is deteriorated; Affect later stage use.
Polymerization pressure be preferably 2.0 ~ 3.5MPa.Required polymerization pressure starts to be by regulating the amount of gaseous state mix monomer to maintain.Polymerization pressure is set in above-mentioned scope, because if pressure is lower than 1MPa, then the monomer concentration of polymerization reaction system is too low, can not reach satisfied speed of reaction.In addition molecular weight can not effectively increase.If pressure is higher than 3MPa, trifluorochloroethylene is more prone to liquefaction, and in small polymerization temperature section, pressure surge is very large, and uncontrollable reactive system steadily carries out.
Preferably, in step (2), in reactor, add perfluorodioxole class monomer and fluorinated olefin monomers, make reactor pressure reach 2.0 ~ 2.5MPa.
The freeze agglomeration of described step (4), washing, drying, pulverizing is: by freezing at-30 ~ 45 DEG C of lower seals for obtained emulsion, then thaw at normal temperatures, be less than or equal to 5 μ S/cm with deionized water washing to specific conductivity, mechanical disintegration under normal temperature after dry.
Carry out sample detection after pulverizing, the particle diameter obtained is less than 100 μm, and product has better solvability in ester, ketone.
The mode of described freeze agglomeration; be frozen into ice by low temperature by obtaining water in emulsion; the formation of ice limits the pedesis of material particles; destroy the protective membrane of particle surface; resin particle is after thawing; being aggegation sedimentation and water stratification under gravity, which reducing the foreign matter content caused because adding ionogen, ensured the purity of resin.
The present invention has following beneficial effect:
The polymkeric substance that the present invention proposes, second-order transition temperature is greater than 65 DEG C, and particle diameter is less than 120 μm, and limiting viscosity is greater than 1.0dl/g, entirely can be dissolved in conventional ester class and other intensive polar solvents.Solve the problems such as current F23 class fluoropolymer second-order transition temperature is on the low side.Be widely used in military industry, as the binding agent of the binding agent of polymer bonding explosive and the current collector metal of battery.
The novel fluoropolymers that the present invention proposes can first be dissolved in suitable solvent, and then mix with main body explosive, bond, granulation and shaping.Polymkeric substance forms one deck inert polymer coating on blasting explosive granules surface through wetting and spreading, thus realizes the bonding to explosive, to reach the mechanical mechanics property improving explosive and the requirement reducing sensitivity.Such as: the binding agent being used as TATB in PBX (PBX).
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
In embodiment, measure Tg by dynamic thermomechanometry (DMA), in an experiment, test amount of samples is 15 ± 0.1mg, and all DMA temperature rise rates are 1 DEG C/min, air atmosphere, stretch mode.When Young's modulus reduction, out-of-phase modulus rise, there is maximum value in Tan, and now corresponding temperature can be used as the characteristic temperature of glass transition.
Solvability: by dried polymer dissolution in ethyl acetate
Limiting viscosity: water bath with thermostatic control temperature controls at 25 ± 0.1 DEG C, adopts the limiting viscosity of determination of ubbelohde viscometer polymkeric substance.
Cl content: adopt GB GB/T 7139-2002 testing method.
Measure fusing point (Tm) by dsc (DSC): with the nitrogen protection of flow velocity 30ml/min, liquid nitrogen is low temperature refrigerant, carries out the test of-10 DEG C ~ 180 DEG C of temperature ranges.Because sample test amount and temperature rise rate can have influence on test result, test amount of samples and be 15 ± 0.1mg in experiment, test temperature rise rate is 10 DEG C/min.Utilize the routine analyzer of DSC to analyze curve, adopt the melt temperature (Tm) of summit temperature as sample of endotherm(ic)peak.
In embodiment, if no special instructions, the technique means adopted is technique means known in the field.
Embodiment 1
In the 50L stainless steel cauldron with agitator, add deionized water 30L, drum nitrogen deoxygenation three times, be evacuated to oxygen level and be less than or equal to 25ppm, add 60g fluorine-containing emulsifier ammonium perfluorocaprylate, whiteruss 400ml (being liquid under normal temperature), open and stir, speed 200rpm, is warming up to 60 DEG C, adds 85% trifluorochloroethylene, 8% vinylidene and 7%PDD mix monomer to 2.0MPa.
After system stability, add 9g Potassium Persulphate, 3g S-WAT, 15g sodium acetate, 30g ethanol, start polyreaction.Constantly add mix monomer simultaneously and keep reactor pressure 3.5MPa, until emulsion solid content reaches 30% stopped reaction in reactor.
Reclaim unreacted monomer, release polymer emulsion, filter paraffin and other impurity, obtained emulsion is sealed freezing in-40 DEG C of freezing alcohol troughs, then thaws at normal temperatures; Outwell clear water, be less than or equal to 5 μ S/cm with deionized water washing to mother liquor specific conductivity, 120 DEG C of vacuum drying ovens dryings 24 hours, mechanical disintegration under normal temperature, carried out detection sample.Test result is in table 1.
Embodiment 2
In 50L reactor, add deionized water 30L, drum nitrogen deoxygenation three times, be evacuated to oxygen level and be less than or equal to 25ppm, add 60g fluorine-containing emulsifier Sodium perfluorooctanoate, whiteruss 400ml (being liquid under normal temperature), open and stir, speed 200rpm, is warming up to 55 DEG C, adds 85% trifluorochloroethylene, 14.9% vinylidene and 0.1%PDD mix monomer to 2.0MPa, after system stability, add 4g Potassium Persulphate and 5 ammonium persulphate composite initiators, 3g Sodium Metabisulfite, 25g sodium acetate, 10g diethyl malonate, start reaction.Start polyreaction.Constantly add mix monomer simultaneously and keep reactor pressure 3.5MPa, until emulsion solid content reaches 30% stopped reaction in reactor, reclaim unreacted monomer, release polymer emulsion, filter paraffin and other impurity, obtained emulsion is sealed freezing in-40 DEG C of freezing alcohol troughs, then thaws at normal temperatures; Outwell clear water, be less than or equal to 5 μ S/cm with deionized water washing to mother liquor specific conductivity, 120 DEG C of vacuum drying ovens dryings 24 hours, mechanical disintegration under normal temperature, carried out detection sample.Test result is in table 1.
Embodiment 3
Repeat the step described in embodiment 1, just add 12g potassium permanganate initiator and 12g oxalic acid, simultaneously 85% trifluorochloroethylene, 5% vinylidene and 10%PDD mix monomer.The results are shown in table 1.
Embodiment 4
Repeating step described in embodiment 1, is just 80% trifluorochloroethylene, 15% vinylidene and 5%PDD mix monomer mix monomer ratio.The results are shown in table 1.
Embodiment 5
Repeat step described in embodiment 1, be just 75% trifluorochloroethylene, 25% vinylidene and 5%PDD mix monomer mix monomer ratio, the results are shown in table 1.
Embodiment 6
Repeat step described in embodiment 1, be just 85% trifluorochloroethylene, 14% vinylidene and 1%PDD mix monomer mix monomer ratio, the results are shown in table 1.
Comparative example 1
Repeat step described in embodiment 1, mix monomer ratio is adjusted to 80% trifluorochloroethylene and 20% vinylidene, and do not add modified monomer PDD, other are constant, obtains the results are shown in table one.
Comparative example 2
Repeat step described in embodiment 1, be just 65% trifluorochloroethylene, 15% vinylidene and 20%PDD mix monomer mix monomer ratio, the results are shown in table 1.
Table 1 the performance test results
From the above results, adopt synthetic method of the present invention, the second-order transition temperature of the novel fluorine compound of gained is greater than 65 DEG C, and limiting viscosity is greater than 1.0dl/g, entirely can be dissolved in conventional ester class and other intensive polar solvents.Be widely used in military industry, as the binding agent of the binding agent of polymer bonding explosive and the current collector metal of battery.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. a fluoropolymer for perfluorodioxole modification, is characterized in that, the general formula of described perfluorodioxole is:
Wherein R '
frepresent that RF or ORF, described RF are the perfluoroalkyl of the linear of C1-C5 or branching, X
1and X
2be F or CF independently of each other
3;
Described fluoropolymer is that fluorinated olefin monomers is polymerized the multipolymer obtained, and it is two or more that described fluorinated olefin monomers is selected from vinyl fluoride, vinylidene, trifluoro-ethylene, tetrafluoroethylene, trifluorochloroethylene, tetrafluoroethylene, tetrafluoeopropene, five fluorine propylene, R 1216, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether;
Described fluorinated olefin monomers accounts for 80 ~ 99.1% of the monomer mass carrying out copolymerization.
2. fluoropolymer according to claim 1, it is characterized in that, described fluorinated olefin monomers is trifluorochloroethylene and vinylidene, and trifluorochloroethylene, vinylidene, perfluorodioxole account for 65 ~ 85%, 5 ~ 25% and 0.1 ~ 20% of the monomer mass carrying out copolymerization.
3. the method for the fluoropolymer of preparation described in claim 1 or 2, is characterized in that, comprise step:
(1) in reactor, add water, fluorine-containing emulsifier, described water accounts for the 40-70% of reactor volume,
(2) in reactor, add perfluorodioxole class monomer and fluorinated olefin monomers, make reactor reach the pressure of polyreaction; In reactor, add PH conditioning agent, chain-transfer agent, initiator and reductive agent, at 30 DEG C ~ 100 DEG C temperature and 1.0 ~ 6.0MPa pressure, carry out polyreaction;
(3) segmentation or add perfluorodioxole class monomer and fluorinated olefin monomers constantly in reactor, maintenance polymerization pressure is 1.0 ~ 6.0MPa, and the solid content reacting liquid phase to reactor is 25-35%, obtains polymerized emulsion;
(4) polymerized emulsion is carried out freeze agglomeration, washs, dry, pulverize, packs.
4. method according to claim 3, it is characterized in that, described fluorine-containing emulsifier is Perfluorocaprylic Acid dipersant, is selected from one or more in Sodium perfluorooctanoate, ammonium perfluorocaprylate or Potassium perfluorooctanoate, and the amount of described fluorine-containing emulsifier is containing 0.001 ~ 4 weight part in every 100 weight parts waters.
5. method according to claim 3, is characterized in that, in described step (1), also in water, adds whiteruss or hydrocarbon ils, adds according to 1 ~ 5% of volume of water.
6. method according to claim 3, is characterized in that, described pH adjusting agent is the one in dipotassium hydrogen phosphate, Sodium phosphate dibasic, sodium acetate, borax and sodium bicarbonate;
Described chain-transfer agent is one or more in ethanol, acetone, chloroform, ethyl acetate, diethyl malonate, and the amount of described chain-transfer agent is containing 0.05 ~ 5 weight part in every 100 weight parts waters.
7. method according to claim 3, it is characterized in that, described initiator is one or more in ammonium persulphate, Potassium Persulphate, potassium permanganate, peroxysuccinic acid, cumene peroxide, dialkyl group peroxycarbonates, and the amount of described initiator is containing 0.01 ~ 6 weight part in every 100 weight parts water media.
8. method according to claim 3, it is characterized in that, described reductive agent is one or more in S-WAT, Sodium Metabisulfite, oxalic acid, iron protochloride, clorox, and the amount of described reductive agent is containing 0.01 ~ 6 weight part in every 100 weight parts water media.
9., according to the arbitrary described method of claim 3 ~ 8, it is characterized in that, described polymerization reactor control carries out at 30 DEG C ~ 80 DEG C temperature and 2.0 ~ 3.5MPa pressure.
10. according to the arbitrary described method of claim 3 ~ 8, it is characterized in that, the freeze agglomeration of described step (4), washing, drying, pulverizing is: by freezing at-30 ~ 45 DEG C of freezing alcohol trough lower seals for obtained emulsion, then thaw at normal temperatures, 5 μ S/cm are less than or equal to specific conductivity with deionized water washing, after drying, mechanical disintegration under normal temperature.
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| CN107986926A (en) * | 2017-11-29 | 2018-05-04 | 中国工程物理研究院化工材料研究所 | High solid loading TATB base aluminum composition modeling powders and preparation method thereof |
| RU2690460C1 (en) * | 2018-10-24 | 2019-06-03 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Membrane for separation of methane-containing gas mixture and method of its production |
| CN114085309A (en) * | 2021-11-22 | 2022-02-25 | 浙江巨化技术中心有限公司 | Solution polymerization preparation method of perfluorosulfonic acid resin |
| CN114213569A (en) * | 2021-11-22 | 2022-03-22 | 浙江巨化技术中心有限公司 | Suspension polymerization preparation method of perfluorosulfonic acid resin |
| CN114276482A (en) * | 2021-11-22 | 2022-04-05 | 浙江巨化技术中心有限公司 | Emulsion polymerization preparation method of perfluorosulfonic acid resin |
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| RU2690460C1 (en) * | 2018-10-24 | 2019-06-03 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Membrane for separation of methane-containing gas mixture and method of its production |
| CN114085309A (en) * | 2021-11-22 | 2022-02-25 | 浙江巨化技术中心有限公司 | Solution polymerization preparation method of perfluorosulfonic acid resin |
| CN114213569A (en) * | 2021-11-22 | 2022-03-22 | 浙江巨化技术中心有限公司 | Suspension polymerization preparation method of perfluorosulfonic acid resin |
| CN114276482A (en) * | 2021-11-22 | 2022-04-05 | 浙江巨化技术中心有限公司 | Emulsion polymerization preparation method of perfluorosulfonic acid resin |
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