CN102007151B - Alkylketone fluorotelomers, methods for the production thereof (variants) and a method for producing functional coatings based thereon - Google Patents

Alkylketone fluorotelomers, methods for the production thereof (variants) and a method for producing functional coatings based thereon Download PDF

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CN102007151B
CN102007151B CN200880128711.XA CN200880128711A CN102007151B CN 102007151 B CN102007151 B CN 102007151B CN 200880128711 A CN200880128711 A CN 200880128711A CN 102007151 B CN102007151 B CN 102007151B
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tfe
telogen
telomer
coating
alkyl ketone
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CN102007151A (en
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D·P·基留欣
I·P·基姆
V·M·布兹克
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INSTITUT PROBLEM KHIMICHESKOI FIZIKI ROSSIISKOI AKADEMII NAUK (IPKHF RAN)
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F114/18—Monomers containing fluorine
    • C08F114/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene

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Abstract

The invention relates to producing agents which are used for forming coatings which exhibit the properties intrinsic to polytetrafluoroethylen, i.e., resistance to chemical aggressive media, antifriction and water-repellent properties, in particular to fluor-contaning telomers and to methods for producing coatings based thereon. The inventive method for producing alkylketone fluorotelomers involves carrying out a free-radical telomerisation reaction of unsaturated perfluorolefins (for example tetrafluoroethylene TFE) in a telogen liquid medium with the ratio of TFE/telogen 0.5-20/100. In the preferred variant, the reaction is carried out with the ratio of TFE/telogen (0.7-3)/100 in such a way that a telomer colloidal solution is formed, which solution is used for applying heat-resistant highly-adhesive coatings the thickness of which ranges from 1 to 5 mkm.

Description

Alkyl ketone fluorine telomer, its preparation method (variant) and preparation are based on the method for its functional coating
Invention field
The present invention relates to generate the material for the manufacture of coating, it has the intrinsic characteristic of tetrafluoroethylene, and namely chemically-resistant environmental attack, resistance to abrasion and water-repellancy more particularly, relate to fluorinated telomer and preparation based on the method for its coating.
Description of the Prior Art
Tetrafluoroethylene (TFE) telomer and use lipid acid, alcohol, aldehyde, ester, halogen and sulfone are well-known [http./www.ta2238/2007 as the method that telogen prepares it; DE3219004, C1,1984; DE 3915759, A1,1990; S.Kotov, G.Kostov, E.Balbolov, React.Kinet.Catal.Lett., volume 63,1 (1998) 107; I.Wlassics and V.Tortelli, Journal of Fluorine Chemistry, volume 127, in February, 2,2006 phase, page or leaf 240].Such telomer is widely used as the intermediate of synthetic fluorochemical, surface active cpd and wormer.
Present method comprises the telomerization of lower perfluoroolefine (for example TFE) and various telogens.
Usually, by chemical free radical initiator [http./www.ta2238/2007; DE3219004, C1,1984; DE 3915759, A1,1990; S.Kotov, G.Kostov, E.Balbolov, React.Kinet.Catal.Lett., volume 63,1 (1998) 107; I.Wlassics and V.Tortelli, Journal of Fluorine Chemistry, volume 127, in February, 2,2006 phase, page or leaf 240] or by ionizing rays [US 3235611, PC 260-653.1,1966] initiation telomerization process.
In [http./www.ta2238/2007], following data about various fluorine telomers have been proposed:
(1) perfluor alcohol is interesting as the base mateiral of pharmacopedics and agrochemistry.CF 2OH and CFOH group are unsettled, and are decomposed into hydrogen fluoride and fluoridize carboxide, produce the perfluor alcohol adducts with amino (Cheburkov and Lillquist, 2002): RFCF 2O -HNEt 3 +(RF:F, C 2F 5I-C 3F 7).
(2) has amino fluorine telomer sulfonate (FTS) F (CF 2) 6-10SO 3 -(FTSA).There are not mp and Vapor pressure data.
(3) fluorine telomer acid: F (CF 2) 6-10CH 2CH 2CO 2 -The mp=87.8 of FTCA ℃ (8: 2).The mp=106.6 of FTUCA ℃ (8: 2).
(4) fluorine telomer alcohol: F (CF 2) 6-10CH 2CH 2OH.There are not the mp data.Vapour pressure: 0.876kPa (6: 2); (0.227kPa 8: 2).
(5) fluorine telomer aldehyde (FTAL): F (CF 2) 6-10CH 2CH 2CHO.There are not the mp data.Vapour pressure: 0.067kPa (8: 2).
(6) fluorine telomer iodide and alkene: FT iodide F (CF 2) 6-10CH 2CH 2I; FT alkene F (CF 2) 6-10CH=CH 2mp＝80℃。
General formula is H (CF 2CF 2) nCH 2The fluoroalkanol of OH (n=1-4) is the intermediate of more synthetic compounds and heat-staple fluoro-containing coating, high temperature lubricant and heat-carrying agent, medicine etc.The key step of its preparation method is included in the free poly tone reaction of TFE and methyl alcohol under the existence of initiator, and [DE 3219004, C1,1984; DE 3915759, A1,1990].In [S.Kotov, G.Kostov, and E.Balbolov, React.Kinet.Catal.Lett., volume 63,1 (1998) 107] paper, in the presence of azo isobutyronitrile (AIBN), carry out the free poly tone reaction of TFE and methyl alcohol.With 0.5-2.0g TFE and 5cm 3Methyl alcohol and 0.05-0.06gAIBN join 12cm 3The steel ampoule in.After removing trace oxygen, the ampoule inclusion is placed room temperature, then be heated to 70 ℃.After removing unreacted TFE, analyzing liquid mixture on gas-chromatography.Separate low molecular volume production thing: H (CF 2CF 2) nCH 2OH, wherein n=1-3; 1H, 1H, 3H-tetrafluoro-1-propyl alcohol (109 ℃ of bp); 1H, 1H, 5H-octafluoro-1-amylalcohol (141 ℃ of bp), and 1H, 1H, 7H-12 fluoro-1-heptanols (170 ℃ of bp).The molecular formula of the wax-like telomer of remaining high molecular is H (CF 2CF 2) nCH 2OH, wherein n＞3.In [I.Wlassics and V.Tortelli, Journal of Fluorine Chemistry, volume 127, in February, 2,2006 phase, page or leaf 240] paper, according to type, the TFE pressure and temperature of initiator and telogen, studied C 2F 4(TFE) and the telomerization of bromine chlorine fluoroethane.Dibromo halo ethane and C that superoxide causes 2F 4Between telomerization, provide α, ω-dibromo perfluoro alkane Br (CF 2) nBr's is synthetic, n=2 wherein, and 4,6, or 8.The importantly selection of telogen and its ability as the bromine donor in the free poly tone reaction.These perfluoroalkyl dibromide are used as derivative (for example fluoridized one and diolefine Br (CF 2) nCH=CH 2And CH 2=CH (CF 2) nCH=CH 2) intermediate.
US 3235611 has described the method for preparing the tetrafluoroethylene telomer in the presence of the chlorinated hydrocarbon telogen by radical polymerization.Available initiator is X-ray or gamma-radiation and fast electronics.As a result, obtained to have general formula Cl 2C=CCl (C 2F 4) nThe telomer of Cl, wherein 2≤n≤20.
In [US 5908966,1999], describe the telomerization process of preparation fluoro-alkyl iodide telomer, comprised the telomerization of poly-fluoroalkyl iodide and unsaturated polyester fluoroolefin or monochloro alkene.The journey of correcting one's mistakes is included in about 300-400 ℃ the temperature range, with poly-fluoroalkyl iodide unsaturated olefin is made an appointment with (1.1-1.9): 1 mol ratio, make poly-fluoroalkyl monoiodide or diiodide (linear or side chain, and on chain chloride and/or bromine, and/or ether oxygen or functional group) contact with unsaturated perfluoroolefine or a chlorine perfluoroolefine.
Described the formation of the cross-linkable composition that is used for protection optical fiber in [US 5690863,1997], it has improved optics, machinery, stickiness and fire resistance characteristic.Silicon optical fiber or plastics composite are comprised of bi-material, i.e. photoconduction fibre core and covering.Usually, the difference of specific refractory power is larger between fibre core and the covering, and the characteristics of luminescence of optical fiber is better.Use general formula to be CH 2The height of=C (R) COOCHXY is fluoridized single functional group propenoic acid ester or methacrylic ester, and wherein R is H or methyl, and X is CF 3Or H, the annex condition is that Y is (CH so if X is H 2) n(CF 2) mZ, wherein Z is F or H, n=0-4, and m=1-10.
Be the tetrafluoroethylene telomer according to technical spirit and the institute result that obtains and the immediate prior art of the present invention, and in the presence of telogen (it is aliphatic ketone or carboxylic acid amide), pass through 60Co gamma rays or chemical initiator initiation prepare its method [USSRAuthors ' Certificate SU is open on January 27th, 665747,2008, Byull.Izobret.No.3] via the free poly tone reaction.
Disclosed method has generated mean chain length and has been no more than n among the SU 665747 Avg=5.5 short chain telomer.Only generated a small amount of telomer with larger n value (6＜n＜20) by aforesaid method; Especially, only obtain the telomer with 10＜n＜20 of trace.The telomerization product, it mainly is the short chain telomer, has low thermostability, because so the boiling temperature of the compound of short chain generally is lower than 200 ℃, therefore, do not allow to make the high-strength coating of high temperatures, and limited it as the application that generates protective coating.
About coating manufacturing and the immediate prior art of the present invention be as in people such as [, Fluoroplastics, Leningrad:Khimiya, 1960, page or leaf 153-180] D.D.Chegodaev the method for the stable Teflon-4D aqeous suspension of preparation.The suspension for preparing by polyreaction acquisition dispersion is unsettled, and condenses easily, and need add immediately tensio-active agent once preparation.Then, concentrated described product in whizzer.In order to prepare business-like suspension, then concentrated throw out is added into water and more tensio-active agent.Therefore, the process of the such suspension of preparation be effort and comprise a lot of steps.After needing guarded surface to coat such emulsion, at 350-380 ℃ of lower sintering, to obtain whole coating, impurity emulsifying agent and stablizer are burnt simultaneously with described coating.This technology can not prepare thickness less than the uniform coating of 20 μ m.And residual cracking emulsifying agent has polluted described coating, and has destroyed its chemical stability and electrical insulation characteristics.By above-mentioned technology, only reach 10 layers through continuous coating, just can use suspension to prepare continuous flawless coating, the minimum thickness of layer can not be less than 10 μ m simultaneously.
Above-mentioned coating coating procedure comprises many steps, demanding thermal treatment temp, and the thickness of gained coating is at least 10 μ m.This characteristic of suspension has been dwindled its range of application, and reality has limited it simultaneously as the application of the lip-deep chemically stable coating of complex construction (for example, on sandstone).
Summary of the invention
The objective of the invention is to prepare novel alkyl ketone fluorine telomer, it can produce strong heat-staple micron thickness coating at the base material of multiple crude substance and structure (such as sandstone, timber, glass, fiber etc.).
Can realize this purpose by the present invention, it is R that the present invention has required general formula 1(CF 2-CF 2) nR 2Alkyl ketone fluorine telomer, wherein n is integer, preferred 1-20, and R 1And R 2It is alkyl ketone molecular structure part.By the concentration of TFE in the choice reaction mixture, namely pass through to change the ratio of TFE/ telogen, but its variation range is (0.5-20)/100, can control the chain length of described fluorine telomer.
Further, by in the liquid phase medium of telogen, under the temperature of the aerodynamic efficiency that process is provided, the method for preparing alkyl ketone fluorine telomer through the free poly tone reaction of carrying out unsaturated perfluoroolefine (for example tetrafluoroethylene), can realize this purpose, wherein said free radical reaction by ionizing rays (for example 60The Co gamma-quanta) cause, TFE/ telogen mol ratio=(0.5-20)/100 wherein, then by currently known methods from reaction mixture separate targets product.
By in the liquid phase medium of telogen, prepare the method for fluorine telomer alkyl ketone through the free poly tone reaction of carrying out unsaturated perfluoroolefine (for example tetrafluoroethylene), also can realize this purpose, wherein under the decomposition of initiator temperature, cause described free radical reaction by chemical initiator, wherein initiator/TFE/ telogen mol ratio=0.5/ (0.5-20)/100.
Further, can realize this purpose by the method for preparing based on alkyl ketone fluorine telomer coating, the method comprises that the component that will contain polymkeric substance is coated to base material, then drying and thermal treatment, wherein chemical pure telomer solution is applied on the base material of various natural goodses, various structure and various size, and wherein heat-treats in 180-200 ℃ temperature range until obtain the uniform coating of quality.
Detailed Description Of The Invention
Essence of the present invention comprises following content.
" telomerization process " refers to the chemical reaction that caused by free radical, and wherein one or more polymerisable molecules join in the molecule that another kind is called telogen.The telomerization process instance that the application provides is the reaction of ketone (telogen) and fluorinated olefin, for example tetrafluoroethylene (TFE):
CH 3COCH 3+nCF 2＝CF 2--＞R 1(CF 2＝CF 2) nR 2，
Wherein n is integer, preferred 1-20, and R 1And R 2It is the ketone molecular structure part that forms by the free poly tone reaction.If described ketone is acetone, for example, R 1And R 2Structure division is H, CH 3, COCH 3Or CH 2COCH 3If described ketone is methylethylketone, these structures can be H, CH 3, CH 2CH 3, COCH 3, COCH 2CH 3, CH 2COCH 2CH 3Or CH 3COCH 2CH 2
The mol ratio of TFE/ ketone is (0.5-20)/100.Described telomerization process is carried out in liquid phase, and wherein TFE is dissolved in telogen.When using radiation to cause, described process is at room temperature carried out [US 3235611, PC 260-653.1,1966].When using chemical initiator, the temperature of described process is the decomposition temperature of initiator, and its scope is 80-100 ℃ of [DE, 3219004,1984; DE, 3915759,1990; S.Kotov, G.Kostov, and E.Balbolov, React.Kinet.Catal.Lett., volume 63,1 (1998) 107; I.Wlassics and V.Tortelli, Journal of Fluorine Chemistry, volume 127, in February, 2,2006 phase, page or leaf 240; The Chemical Encyclopedic Dictionary, Moscow:Sovetskaya Entsiklopedia, 1983,562pp.].TFE experiences under these conditions fully and transforms.
Usually, telomerization generates the mixture of the poly-fluoroalkyl ketone with wide molecular weight distribution, and non-single compound.The molecular weight distribution of described product depends on the TFE concentration in the reaction mixture.The gel permeation chromatography of the telomerization product that directly carries out in reaction mixture shows, be (0.5-0.7)/100 o'clock for TFE/ ketone ratio, and generation has the lower molecular weight telomer of chain length n=1-8; Their mean chain length n Avg＜6.When TFE/ ketone ratio was (0.7-3)/100, the preferred generation had the telomer that chain length is 1＜n＜20; Their mean chain length n Avg=6-15.When TFE/ ketone ratio was (3-20)/100, formation had mean chain length n AvgThe telomer of=15-20; When TFE/ ketone ratio surpassed 20/100, telomer had mean chain length n Avg＞20.
Thus, according to the concentration that contains TFE in the reactive ketone mixture, the free poly tone reaction produces:
(1) having mean chain length is n Avg＜6 limpid colourless telomer true solution (TFE/ ketone is (0.5-0.7)/100);
(2) having mean chain length is 6＜n AvgThe telomer colloidal solution of＜15 oyster white viscosity (0.7/100＜TFE/ ketone＜3.0/100);
(3) having mean chain length is 15＜n AvgThe directed phase (0.3/100＜TFE/ ketone≤20/100) of＜20 the telomer solution that is shown as viscous gel;
(4) having mean chain length is n Avg＞20 viscous gel (being actually polymerization) telomer solution (TFE/ ketone＞20/100).
The IR spectrum of dry telomer is 1211 and 1154cm -1The place shows as CF 2The characteristic peak that group is strong, and 1734cm -1The characteristic peak of zone=C=O group.These peaks are observed in test the fact with enough intensity, have shown a large amount of end groups, but and the CF of the short length of direct representation 2Molecular chain.The end group of chain is ketone molecular structure part.
The thermogravimetric analysis of dry telomer shows, according to the concentration of TFE in the initial action mixture, 100-500 ℃ of scope strong weightlessness is arranged.Strong weightlessness with lower molecular weight telomer of n≤8 occurs in 100-300 ℃ warm area, because the evaporation in boiling point district.For the telomer with chain length n＞15, weightlessness occurs in and surpasses 400 ℃ more high-temperature zone, because the heat collapse of material.
The atomic force microscope of the coating that is generated by solution studies show that removes the coating that described solvent has generated nanometer size particles from colloidal solution.
Because GPC shows the product that the reaction soln of different initial TFE concentration generates and have different structures, also be supposed to have different structures by from these solution, removing the coating that acetone obtains.When the ratio of long-chain increased, the orientation of oligopolymer occured in the solution.As mean chain length n Avg〉=6 o'clock (when being initial TFE concentration increase) forms the aggregate with the colloid nanometer size particles that increases oligopolymer density.When initial TFE concentration further increased, described oligopolymer changed directed phase into, this transformation be similar to the bar body by liquid crystal to row phase transformation.
Desolventizing has generated the layer of different structure from above-mentioned form.Has mean chain length n AvgThe true solution that＜6 telomer forms is transformed into the molecular crystal with low melting temperature, is not suitable for preparing heat-staple high-strength coating.On the other hand, has mean chain length 15＜n AvgThe orientation of＜20 telomer is transformed into the close heap state with high melting temperature (Tm) mutually, does not have enough viscosity.Has mean chain length n AvgThe solution of＞20 telomer is suitable for the coating of coating hardly, because it has weak adhesivity to the surface that is employed coating, and described coating can be removed under little mechanical effect.Colloidal solid, the density of wherein said oligopolymer are higher than true solution but are lower than the telomer of directed phase, can produce strongly adherent and heat-staple coating.
Thermogravimetric analysis (DTG) shows by having mean chain length n AvgThe coating that the true solution of＜6 fluorine telomer acetone generates is volatilized when being heated to 200-250 ℃ fully.By having mean chain length n AvgThe coating that the solution of＞15 fluorine telomer generates has the highest thermostability (＞400 ℃), but sticks poor performance, and is easy to mechanically remove.Optimum coating is by having mean chain length 6＜n Avg＜15 solution generates, 400 ℃ at the most of thermostabilitys, and it is satisfactory to stick performance.
Under radiation caused, described process was at room temperature carried out.When using chemical initiator, the temperature of described process is the decomposition temperature of initiator, and its scope is 80-100 ℃.TFE has experienced completely and has transformed under these conditions.
After removing acetone, the white solid matter that stays can be obtained the characteristic of resistance to abrasion, thermostability and hydrophobic value close to PTFE by its protective coating that makes.
Method of the present invention provides the thin protective coating that has close to the characteristic of PTFE, because thin (1-5 μ m is thick) coating only obtains from solution, has therefore enlarged the range of application of fluorine-containing coat.The method is included under the existence of telogen and prepares the tetrafluoroethylene telomer by the free poly tone reaction, then the solution with described fluorine telomer is coated on the surface that wish is processed, oven dry is to remove unreacted telogen, and the residuum of thermal treatment drying under 180-200 ℃ temperature, this processing causes the telomer fusing, simultaneously lower-molecular-weight component (n≤5) volatilization stays and has n＞more dystectic component of 6, and wherein said telogen uses aliphatic ketone.
Except the broadened application scope, carry out the coating coating by solution and simplified the film generation technique, because solution can be in encloses container almost stored indefinitely in the existence range of solvent liquid phase medium, and the thermal treatment after applying is lower but not carry out under 350-380 ℃ at 180-200 ℃.Film thickness is 1-5 μ m, and the treatment time is inessential, but it is very important to the thin film coated of this temperature sensitive material and to using the thin film coated of Portable heating mode under the condition of unsteady state.
Some embodiment have below been provided so that essence of the present invention to be described.
Embodiment 1
With the chemical pure grade acetone in the sealed reactor on vacuum apparatus exhaust to remove dissolving air wherein.After adding TFE take the mol ratio of itself and the acetone amount as 0.5/100, with described reactor sealing.By 60The radiation of Co gamma-quanta is at room temperature carried out, and total dose is 20kGy.It is completely that TFE transforms; The unreacted gaseous state TFE of $ emits when opening reactor.
Described reaction product is shown as limpid colourless solution.The degree that is presented at TFE polymerization in this solution by the definite molecular weight distribution of gel permeation chromatography is n Avg≤ 4.The residuum of removing the drying behind the acetone can be dissolved in acetone fully.The IR spectrum of removing the telomerization product behind the acetone shows as C-F 2The strong Absorption Characteristics peak of group and the more intense peak relevant with carbonyl, the latter and C-F 2The peak matches, and shows the formation of oligomeric TFE chain.
The thermogravimetric analysis of dry telomer shows n Avg≤ 4, and the strong weightlessness in the 150-200 ℃ of temperature range relevant with volatilization in the material boiling section.
Embodiment 2
According to embodiment 1 described described process, wherein TFE/ acetone mol ratio=1/100 of carrying out.
Described reaction product shows as colloidal solution.The degree that is presented at TFE polymerization in this solution by the definite molecular weight distribution of gel permeation chromatography is n Avg=8.The residuum of removing the drying behind the acetone dissolves in acetone.The IR spectrum of removing the telomerization product behind the acetone shows as CF 2The strong Absorption Characteristics peak of group and the more intense peak relevant with carbonyl, the latter and CF 2The peak matches, and shows the formation of oligomeric TFE chain.
The thermogravimetric analysis of dry telomer has shown the strong weightlessness in the 150-300 ℃ of temperature range relevant with volatilization in the material boiling section.
Embodiment 3
According to embodiment 1 described described process, wherein TFE/ acetone mol ratio=5/100 of carrying out.It is completely that TFE transforms; When opening reactor, there is not unreacted gaseous state TFE to emit.
Described reaction product is shown as milky white colourless viscosity colloidal solution.The degree that is presented at TFE polymerization in this solution by the definite molecular weight distribution of gel permeation chromatography is n Avg=15.The dry residue of removing behind the acetone is dissolved in acetone hardly; Be lower than 10% and enter solution.The IR spectrum of removing the telomerization product behind the acetone shows as CF 2The strong Absorption Characteristics peak of group and the more intense peak relevant with carbonyl.
Thermogravimetric analysis has shown that in the strong weightlessness that surpasses under 400 ℃ the temperature possibility is because the thermolysis of described material.
Embodiment 4
According to embodiment 1 described described process, wherein TFE/ acetone mol ratio=10/100 of carrying out.It is completely that TFE transforms; When opening reactor, there is not unreacted gaseous state TFE to emit.
Described product is shown as the gel of thickness, and this moment, the GPC test was impossible.DTG has only shown the thermolysis that surpasses under 500 ℃ the temperature, just as PTFE.
Embodiment 5
Carry out described process according to embodiment 2 is described, the methylethylketone of chemical pure level is used as telogen.Described product is similar to the product of embodiment 2.
Embodiment 6
To put into glass ampoule and be dissolved in 1% benzoyl peroxide (C of acetone 6H 5CO-O-) 2(decomposing fusing at 106-107 ℃) solution exhaust on vacuum apparatus is to remove dissolving air wherein.After with the amount that obtains on request TFE/ acetone mol ratio=2/100 TFE being added to ampoule, be heated to 100 ℃ with the ampoule sealing and with 5 hours.After described process is finished, formed limpid colourless viscous soln.The polymer yield that weight measurement is determined is about 70%.
The IR spectrum of removing the telomerization product behind the acetone shows as CF 2Strong Absorption Characteristics peak and the peak relevant with carbonyl of group.
Embodiment 7
According to embodiment 6, under 100 ℃ temperature, carried out described process 4 hours, use the 2% ditertiary butyl peroxide (CH that is dissolved in acetone 3) C-O-O-C (CH) 3(decomposition temperature is 80-130 ℃) solution, TFE/ acetone mol ratio=2/100.Obtained colourless viscous colloidal solution, the polymer weight productive rate is about 60%.
The IR spectrum of removing the telomerization product behind the acetone shows as CF 2Strong Absorption Characteristics peak and the peak relevant with carbonyl of group.
Embodiment 8
According to embodiment 6, under 80 ℃ temperature, carried out described process 2 hours, use the 1% 2 cyclohexyl peroxy dicarbonate C that is dissolved in acetone 6H 11OCO-O-O-OCOC 6H 11(decomposition temperature is 65-70 ℃) solution, TFE/ acetone mol ratio=2/100.Obtained colourless viscous colloidal solution, the polymer weight productive rate is about 60%.
The IR spectrum of removing the telomerization product behind the acetone shows as CF 2Strong Absorption Characteristics peak and the peak relevant with carbonyl of group.
Embodiment 9
According to embodiment 6, under 100 ℃ temperature, carried out described process 1 hour, use to be dissolved in 1%2 of acetone, 2-Diisopropyl azodicarboxylate (CH 3) 2C (CN) N=N (CN) (CH 3) 2(decomposition temperature is 105-106 ℃) solution, TFE/ acetone mol ratio=2/100.Obtained colourless viscous colloidal solution, the polymer weight productive rate is about 30%.
Embodiment 10
The 100g river sand with the telomer solution impregnation of about 50ml according to embodiment 2 preparation, and is dried to constant weight under 50 ℃.The weight of described polymkeric substance reaches the 0.28wt% of sand, and the one-tenth-value thickness 1/10 that obtains coating according to the specific surface area of sand is the hundreds of nanometer.Sand is behind 180 ℃ of lower heating 10min, and the not wetting grains of sand swim in the water.
The 4-ml portion is put into the P1R-41 fritted glass filter of diameter 25mm by the sand of above-mentioned processing, and flood with 10ml distilled water.When 15s, detect the beginning of water infiltration, and finish behind the 300s.For untreated sand, when 1s, detect the beginning of infiltration, and finish at 75s.For the strainer of sky, when 1s, detect the beginning of infiltration, and finish at 30s.
Therefore, even so a small amount of fluorinated film makes the surface of described sand have hydrophobic property.
Embodiment 11
Be coated on steel sheet 3 (according to the carbon steel of the normal quality of GOST (Russian national standard) 16523-89) according to the telomer of embodiment 2 preparation.The data of these coatings are listed in table 1, and the coating that forms with varnish F-42 (the fluorine varnish that Kirov-Chepets chemical plant polymer production department produces) compares.
Table 1
Figure BPA00001245490800111
On show really shown the TFE telomer solution than varnish F-42 to the higher hydrophobicity of precoat.
Embodiment 12
Be coated on dull and stereotyped and cotton that glass or timber are made according to the telomer of embodiment 2 preparation.The wetting angle data are listed in table 2.
Table 2
Sample type Coat-thickness, μ m Wetting angle, deg Remarks
Cotton 4 102-130 Coating is inhomogeneous; A plurality of zones by base material obtain data.
Timber 2,3 102-105 Coating is inhomogeneous; A plurality of zones by base material obtain data.
Glass 8 90-100 Coating is inhomogeneous; A plurality of zones by base material obtain data.
On show and show that really telomer TFE coating makes the surface have hydrophobicity.
Embodiment 13
Telomer according to embodiment 2 preparations is coated on the flat board of making based on the sulfurized nitrile rubber of divinyl/paracril 1078 (SKN-18+SKN-26) and V14 (SKN-18) (production of rubber industry institute), simultaneously are being furnished with three ball pressure heads, steel ball size is the friction airborne measurements frictional coefficient of 8mm, fraction time 1min.Coat-thickness is 10-15 μ m.Data are listed in table 3.
Table 3
Sample type Frictional coefficient on the uncoated top coat Frictional coefficient on the coated surface
1078(SKN-18+SKN-26) 0.76-0.91 0.56
V14(SKN-18) 0.87-0.95 0.83
Apply telomer coating and reduced frictional coefficient 10-20%.
Low-molecular-weight polymers is used to protective coating and has the wear-resistant and fire resistance characteristic similar to tetrafluoroethylene.
Embodiment 14
Telomer according to embodiment 1,2 and 4 preparations is coated on (2.5 * 7.5) cm 2Protective glass on, and at room temperature be dried to constant weight.Produced so white coating.Protective glass after coated is 200 ℃ of lower dry 20min in moisture eliminator.The comparative feature of coating is listed in table 4.
Table 4
Figure BPA00001245490800131
On show true demonstration, be thin with hydrophobic according to the coating of the telomer of embodiment 1 preparation, but when heating, stand very large weight loss.Coating according to the telomer of embodiment 2 is heat-staple and hydrophobic.According to the coating shedding of the telomer of embodiment 4 and be not suitable for producing even protective coating.

Claims (6)

1. general formula is R 1(CF 2-CF 2) nR 2The mixture of alkyl ketone fluorine telomer, R wherein 1And R 2Be alkyl ketone molecular structure part, n is integer, and the mean chain length n of fluorine telomer in the mixture wherein AvgBe 6＜n Avg＜15.
2. in the liquid phase medium of telogen, under the temperature of the aerodynamic efficiency that process is provided, generate the method for alkyl ketone fluorine telomer by the free poly tone reaction of finishing tetrafluoroethylene (TFE), wherein said telogen is alkyl ketone, it is characterized in that causing described free radical reaction by ionizing rays, wherein TFE/ telogen mol ratio=(0.7-3.0)/100.
3. the method for claim 2 is wherein passed through 60The Co gamma-quanta causes described free radical reaction.
4. in the liquid phase medium of telogen, generate the method for alkyl ketone fluorine telomer by the free poly tone reaction of carrying out tetrafluoroethylene (TFE), wherein said telogen is alkyl ketone, it is characterized in that under the decomposition temperature of initiator, causing described free radical reaction by chemical initiator, wherein initiator/TFE/ telogen mol ratio=0.5/ (0.7-3.0)/100.
5. by according to claim 3 or the product that generates of 4 method.
6. preparation is based on the method for the coating of alkyl ketone fluorine telomer, the method comprises that the component that will contain polymkeric substance is coated on the base material, then drying and thermal treatment, it is characterized in that the solution of mixture of alkyl ketone fluorine telomer that will be according to claim 1 or the solution of product according to claim 5 are coated on the various natural base materials, and be under 180-200 ℃ temperature, to heat-treat until obtain the coating of homogeneous quality.
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