Fluoropolymer latex, method of producing said fluoropolymer latex and fluoropolymer

FIELD: chemistry.

SUBSTANCE: described is a fluoropolymer latex which contains a fluoropolymer and fluorine-containing emulsifier of formula (1): F(CF2)4OCF2CF2OCF2COOA, where A is a hydrogen atom, alkali metal or NH4. A method is also described for producing such latex, and a fluoropolymer, which is obtained by coagulating fluoropolymer latex. The fluoropolymer latex can be used as an agent for coating different materials, such as metallic substrates, inorganic oxide substrates, polymer substrates, synthetic fibre, glass fibre, carbon fibre or natural fibre.

EFFECT: fluoropolymer is useful as material with excellent heat resistance, oil resistance, chemical resistance, weather resistance, non-stickiness, anti-overgrowth properties, water-repellent properties, oil-repellent properties, solvent-repellent properties.

7 cl, 2 tbl, 14 ex

 

The technical field to which the invention relates

The present invention relates to a latex of polymer stabilized particular fluorine-containing emulsifier, and the method of its production.

Prior art

As described in the U.S. patents 3271341 and Japan And is 2002-317003, the method of polymerization of flarmanager, as such, or copolymerization of flarmanager with another monomer in the mixture in an aqueous environment, using different emulsifiers first widely used and it was also suggested different emulsifiers.

It is known that depending on the type of these emulsifiers, the rate of polymerization of flarmanager, the stability of the latex of the polymer during storage and molecular weight and different physical properties of the fluoropolymer, which must be received change. The polymerization rate of flarmanager and stability of the fluoropolymer latex during storage is still insufficient, and therefore, the desired latex with improved properties.

Description of the invention

Tasks that should be solved by the invention

The present invention is to create a method of obtaining a fluoropolymer latex emulsion polymerization, using a special fluorine-containing emulsifier with excellent performance fluoropolymer latex, and to provide such a fluoropolymer latex. Further, another objective for the present invention - to create a method of obtaining a fluoropolymer latex, in which the resulting latex polymer has excellent storage stability, and to create such a fluoropolymer latex.

That is, the present invention relates to a latex polymer which contains a fluorocarbon polymer and a fluorinated emulsifier represented by the formula (1): F(CF2)nO(CF2CF2O)mCF2COOA (where a is a hydrogen atom, alkali metal or NH4, n is an integer from 3 to 10 and m=0 or an integer from 1 to 3).

Further, the present invention relates to such a latex fluorocarbon resin, in which the fluoropolymer is a copolymer of at least one formanager selected from the group consisting of tetrafluoroethylene (hereinafter referred to as TPV), vinylidenefluoride (hereinafter referred to as WDF), hexaferrite (hereinafter referred to as HFP), CF2=C(ORf)nF2-n(in which Rf- C1-8performanceline or performanceeasy group containing at least one ether linkage in the molecule, n=1 or 2, and each carbon chain may be linear circuit may contain a branched chain or may have a cyclic structure) and chlorotrifluoroethylene (hereinafter referred to as HCFA), if necessary, at least one monomer selected from the group consisting of CH2=CHOR (where R is the 1-8an alkyl group or oxyalkylene group containing at least one ether bond, and any one of the carbon chains may be linear circuit may contain a branched chain or may have a cyclic structure), propylene (hereinafter referred to as P) and ethylene (hereinafter referred to as e) and, if necessary, at most 10 mol.% the monomer containing a crosslinking group.

Further, the present invention relates to such a latex fluorocarbon resin, in which the fluoropolymer is at least one member selected from the group consisting of polymer TPV, TFE/HCFA, TFE/P, TFE/HFP, copolymer WDF/HFP, TFE/WDF/HFP, TFE/CF2=CFOCF3, TFE/CF2=CFOC3F7, TFE/CF2=CFOCF3/CF2=CFOC3F7, TFE/CF2=C(OC2F5)2, TFE/metilidinovy ether (hereinafter referred to as PHE), TFE/ethylenically ether (hereinafter referred to as EVA), TFE/n-butylvinyl ether (hereinafter referred to as BWA), TFE/EVE/BWA, copolymer WDF/CF2=CFOC3F7, copolymer of e/HFP and TFE/P/WDF.

Further, the present invention relates to such a latex fluorocarbon resin, in which the fluoropolymer is at least one member selected from the gr is PPI, consisting of polymer TPV, TFE (40 to 60 mol.%)/P (60 to 40 mol.%), of TFE (40 to 70 mol.%)/CF2=CFOCF3(from 60 to 30 mol.%), of TFE (40 to 70 mol.%)/CF2=CFOC3F7(from 60 to 30 mol.%), of TFE (40 to 70 mol.%)/CF2=C(OC2F5)2(from 60 to 30 mol.%), of TFE (from 70 to 30 mol.%)/PHE (from 30 to 70 mol.%), of TFE (from 70 to 30 mol.%)/EVE (from 30 to 70 mol.%), of TFE (from 70 to 30 mol.%)/BWA (from 30 to 70 mol.%), of TFE (from 60 to 30 mol.%)/EVE (from 1 to 69 mol.%)/BWA (from 1 to 69 mol.%), copolymer WDF (from 40 to 70 mol.%)/CF2=CFOC3F7(from 60 to 30 mol.%), copolymer e (from 40 to 60 mol.%)/HFP (from 60 to 40 mol.%) and TFE (from 30 to 60 mol.%)/P (from 20 to 50 mol.%)/WDF (from 1 to 40 mol.%).

Further, the present invention relates to such a latex fluorocarbon resin, in which the fluorine-containing emulsifier is a compound of the formula F(CF2)nOCF2CF2OCF2COOA (where a is a hydrogen atom, alkali metal or NH4and n=3 or 4).

Further, the present invention relates to a method for producing a latex polymer which comprises emulsion polymerization formanager in an aqueous medium containing 0.001 to 10.0 wt.% fluorinated emulsifier represented by the formula (1): F(CF2)n(CF2CF2O)mCF2COOA (where a is a hydrogen atom, alkali metal or NH4n=an integer of Chisloth 3 to 10 and m=0 or an integer from 1 to 3), to obtain the fluoropolymer latex.

Further, the present invention relates to such a method for producing a fluoropolymer latex, in which the fluoropolymer is at least one copolymer of flarmanager selected from the group consisting of TPV, WDF, GUF,

CF2=C(ORf)nF2-n(where Rf- C1-8performanceline or performanceeasy group containing at least one ether linkage in the molecule, n=1 or 2, and each carbon chain may be linear circuit may contain a branched chain or may have a cyclic structure) and HCFA and, if necessary, at least one monomer selected from the group consisting of CH2=CHOR (R1-8an alkyl group or oxyalkylene group containing at least one ether bond, and any one of the carbon chains may be linear circuit may contain a branched chain or may have a cyclic structure), propylene (hereinafter referred to as P) and ethylene (hereinafter referred to as e) and, if necessary, the copolymer of at most 10 mol.% the monomer containing a crosslinking group.

Further, the present invention relates to such a method for producing a fluoropolymer latex, in which the fluorine-containing emulsifier is a compound of the formula F(CF2)nOCF2CF2OCF2COOA (where a is the volume of hydrogen, alkali metal or

NH4and n=3 or 4).

Further, the present invention relates to a latex of a polymer obtained by concentration of the latex polymer obtained by the method for producing a latex of polymer to the concentration of the fluoropolymer is at least 30 wt.%.

Further, the present invention relates to a fluoropolymer obtained by coagulation of the latex polymer obtained by the method for producing a fluoropolymer latex.

The TECHNICAL RESULT of the INVENTION

According to the method of obtaining the latex polymer of the present invention is achieved by a high rate of polymerization of flarmanager and performance fluoropolymer latex is excellent.

Then, the obtained fluoropolymer latex has excellent storage stability.

The PREFERRED EMBODIMENT of the INVENTION

In the process of obtaining the latex polymer of the present invention flarmanager is subjected to emulsion polymerization in an aqueous medium containing fluorinated emulsifier represented by the formula (1).

As flarmanager, which must be subjected to emulsion polymerization, can be specified by at least one formanager selected from the group consisting of TPV, WDF, HFP, PERFLUORO(alkyl - or alquilervehiculo ether)represented by FD is moloi CF 2=C(ORf)nF2-n(in which Rf- C1-8performanceline or performanceeasy group containing at least one ether linkage in the molecule, n=1 or 2, and each carbon chain may be linear circuit may contain a branched chain or may have a cyclic structure), and HCFA.

Such hormonally can be used as such or in combination of two or more of them.

Further, in addition to the above flarmanager, one or more monomers capable of copolymerization, type CH2=CHOR (R1-8an alkyl group or oxyalkylene group containing at least one ether bond, and any one of the carbon chains may be linear circuit may contain a branched chain or may have a cyclic structure), N or e, can be copolymerizable.

Next, copolymerizing monomer, which will be subjected to emulsion polymerization, may contain, in addition to the aforementioned monomers, at most 10 mol.% the monomer containing a crosslinking group. As examples of such a monomer containing a crosslinking group can be converted to 1-bromo-1,1,2,2-tetrafluorohydroquinone ether (hereinafter referred to as Ugwa), maleic anhydride, itacademy anhydride, maleic acid or taconova acid. The polymerization ratio is anomura, containing a crosslinking group, is from 0.001 to 5 mol.%, particularly preferably from 0.01 to 3 mol.%.

The present invention is characterized by the content of one or more fluorinated emulsifier represented by the formula (1): F(CF2)n(CF2CF2O)mCF2COOA where a is a hydrogen atom, alkali metal or NH4n=an integer from 3 to 10 and m=0 or an integer from 1 to 3).

As the alkali metal to A, for example, can be given lithium, sodium or potassium. As A particularly preferred NH4or sodium, and the most preferred NH4.

The following examples are particularly preferable fluorine-containing emulsifiers can be given, but the preferred emulsifiers are not limited to.

As a specific example, when the a - hydrogen atom, lead C3F7OCF2CF2OCF2COOH, C4F9OCF2CF2OCF2COOH, C5F11OCF2CF2OCF2COOH, C6F13OCF2CF2OCF2COOH, C3F7O(CF2CF2O)2CF2COOH, C4F9O(CF2CF2O)2CF2COOH,

C5F11O(CF2CF2O)2CF2COOH, C6F13O(CF2CF2O)2CF2COOH, C3F7O(CF2CF2O)3CF2COOH, C4F9O(CF2CF2/sub> O)3CF2COOH, C5F11O(CF2CF2O)3CF2COOH or C6F13O(CF2CF2O)3CF2COOH.

As a specific example, when A - lithium, lead C3F7OCF2CF2OCF2COOLi, C4F9OCF2CF2OCF2COOLi, C5F11OCF2CF2OCF2COOLi, C6F13OCF2CF2OCF2COOLi, C3F7O(CF2CF2O)2CF2COOLi, C4F9O(CF2CF2O)2CF2COOLi,

C5F11O(CF2CF2O)2CF2COOLi C6F13O(CF2CF2O)2CF2COOLi, C3F7O(CF2CF2O)3CF2COOLi, C4F9O(CF2CF2O)3CF2COOLi, C5F11O(CF2CF2O)3CF2COOLi or C6F13O(CF2CF2O)3CF2COOLi.

As a specific example, when a sodium, lead C3F7OCF2CF2OCF2COONa, C4F9OCF2CF2OCF2COONa, C5F11OCF2CF2OCF2COONa, C6F13OCF2CF2OCF2COONa, C3F7O(CF2CF2O)2CF2COONa,

C4F9O(CF2CF2O)2CF2COONa, C5F11O(CF2CF2O)2CF2COONa, C6F13O(CF2CF2 O)2CF2COONa, C3F7O(CF2CF2O)3CF2COONa, C4F9O(CF2CF2O)3CF2COONa, C5F11O(CF2CF2O)3CF2COONa or C6F13O(CF2CF2O)3CF2COONa.

As a specific example, when A - potassium, lead C3F7OCF2CF2OCF2COOK, C4F9OCF2CF2OCF2COOK, C5F11OCF2CF2OCFZCOOK, C6F13OCF2CF2OCF2COOK, C3F7O(CF2CF2O)2CF2COOK, C4F9O(CF2CF2O)2CF2COOK,

C5F11O(CF2CF2O)2CF2COOK, C6F13O(CF2CF2O)2CF2COOK, C3F7O(CF2CF2O)3CF2COOK, C4F9O(CF2CF2O)3CF2COOK, C5F11O(CF2CF2O)3CF2COOK or

C6F13O(CF2CF2O)3CF2CO OK.

As a specific example, when A - NH4lead C3F7OCF2CF2OCF2COONH4C4F9OCF2CF2OCF2COONH4C5F11OCF2CF2OCF2COONH4,

C6F13OCF2CF2OCF2COONH4C3F7O(CF2CF2O)2CF2COONH 4C4F9O(CF2CF2O)2CF2COONH4C5F11O(CF2CF2O)2CF2COONH4C6F13O(CF2CF2O)2CF2COONH4C3F7O(CF2CF2O)3C F2COONH4C4F9O(CF2CF2O)3CF2COONH4,C5F11O(CF2CF2O)3CF2COONH4or C6F13O(CF2CF2O)3CF2COONH4.

As the fluorine-containing emulsifiers of the present invention preferred are C3F7OCF2CF2OCF2COONH4C4F9OCF2CF2OCF2COONH4C6F13OCF2CF2OCF2COONH4C4F9O(CF2CF2O)2CF2COONH4C4F9O(CF2CF2O)3CF2COONH4and among them, particularly preferred C3F7OCF2CF2OCF2COONH4and C4F9OCF2CF2OCF2COONH4.

In the present invention, the fluoropolymer latex receive, exposing formanager emulsion polymerization in an aqueous medium containing from 0.001 to 10.0 wt.% fluorine-containing emulsifier. The content of the fluorinated emulsifier in the aqueous medium is preferably from 0.001 to 5 wt.%, especially preferably the t 0.01 to 3 wt.%. The content of the fluorinated emulsifier in the latex of the polymer thus obtained, is preferably from 0.03 to 10 wt.%, particularly preferably from 0.05 to 5 wt.%, in the calculation of the fluoropolymer, and further preferably from 0.001 to 5 wt.%, particularly preferably from 0.01 to 3 wt.%, in the calculation in the aquatic environment.

When the fluorinated emulsifier of the present invention compared with a conventional emulsifier having no ether oxygen, such as perforateed ammonium, or an emulsifier having a structure in which performanceline group branched found that the dynamic surface tension of an aqueous solution having the same concentration becomes low. Accordingly, this leads to the fact that the reactivity of gaseous monomer during the polymerization and the wettability and permeability of the obtained latex of the polymer is high.

Especially in the polymerization reaction of TFE/P or TFE/P/WDF solubility of the gaseous monomer in the aqueous environment is very high compared with the reaction in the presence of performanta ammonium, in accordance with what can be improved performance.

As the polymerization initiator used in the emulsion polymerization may be used an ordinary radical initiator polymer clay is Itachi, especially preferred water-polymerization initiator. As a specific example of such aqueous polymerization initiator may be mentioned a persulfate such as ammonium persulfate, hydrogen peroxide or a redox polymerization initiator comprising a combination of these compounds and a reducing agent, such as hydrosulfite sodium or sodium thiosulfate, inorganic polymerization initiator having a small amount of iron salt is iron(2), silver sulphate or other connection, included in a redox polymerization initiator or organic polymerization initiator, such as peroxide dinternal acid or the dihydrochloride of azobisisobutyronitrile.

The polymerization initiator may be added at the beginning or in the middle of the emulsion polymerization. The amount of the polymerization initiator is preferably from 0.0001 to 3 wt.%, particularly preferably from 0.001 to 1 wt.%, in the calculation of the monomer used in the polymerization.

Polymerization formanager can be used by the transfer agent circuit to control molecular weight.

As transfer agent circuit can be applied to alcohol, such as methanol or ethanol, a chlorofluorocarbon, such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane or 1,1-dichloro-1-foraten, hydrocarbon, that is Oh as pentane, hexane or cyclohexane, Rf2I2(where Rf2- C1-16rich poliferation) or Rf3IBr (where Rf3- C1-16rich poliferation). Rf2I2- preferably 1,4-diiodopentane. Further, Rf3IBr - preferably 1-bromo-4-imperforate.

Conditions of emulsion polymerization upon receipt of the latex polymer of the present invention is selected depending on the type of the desired polymer copolymerization relations fluoropolymers, temperature of decomposition of the polymerization initiator, etc. the Pressure of polymerization is preferably at least from 0 MPa (gauge pressure) up to at most 20 MPa (gauge pressure), particularly preferably at least 0.3 MPa (gauge pressure) to at most 10 MPa (gauge pressure), particularly preferably at least 0.3 MPa to at most 5 MPa. The temperature of polymerization is preferably at least 0°C to at most 100°C, particularly preferably at least 10°C to at most 80°C.

As one of typical examples of fluoropolymers that will be obtained in accordance with the method of obtaining the latex polymer of the present invention can be applied polymer TPV (hereinafter referred to as PTFE).

Here PTFE which engages not only the homopolymer of the TPV, but also modified PTFE, which modify the copolymerization with another co monomer, taken in such a small amount, so as not to cause fluctuation in the melt. As such a co monomer can be brought HFP, HCFA or PERFLUORO(alkylvinyl ether) (hereinafter referred to as PAVE). The number of carbon perforaciones group PAVE is preferably from 1 to 8.

Further, as another typical example of such fluoropolymers can be given the TFE/PAVE, TFE/HFP/PAVE, the TFE/e, TFE/P/WDF or TFE/PAVE. Here the TFE/PAVE means a copolymer obtained by copolymerization of TPV, PAVE, and the same applies to the other copolymers.

The method of obtaining the latex polymer of the present invention is suitable for obtaining the fluoropolymer.

As preferred specific examples of the fluorocarbon resin may be mentioned PTFE, TFE/HCFA, TFE/P, a TFE/HFP copolymer WDF/HFP, TFE/WDF/HFP, TFE/CF2=CFOCF3the TFE/CF2=CFOC3F7the TFE/CF2=CFOCF3/CF2=CFOC3F7the TFE/CF2=C(OC2F5)2the TFE/PHE, TFE/EVE, TFE/BWA, TFE/EVE/BUA copolymer WDF/CF2=CFOCF3that SOPs shall limer e/HFP or a TFE/P/WDF.

The process is especially suitable for the production of PTFE, TFE/P, TFE/P/WDF or TFE/PAVE.

There are no particular restrictions on molar relationships polymerized units in the calculation of the corresponding monomers in the above copolymer, and it may be arbitrarily selected depending on the desired properties. For example, the TFE/P molar ratio of polymerized units per TPV/polymerized units based on P is preferably from 40/60 to 70/30, more preferably from 50/50 to 60/40. Further, in the TFE/PAVE performanceline group HAVE preferably has the number of carbon atoms from 1 to 8 and may contain etheric oxygen atom. This performanceline group can be linear, branched, or mixtures thereof. As perforaciones group a more preferred group of CF3C3F7C3F7OC3F6or C3F7OC3F6OC3F6.

Further, in the TFE/PAVE the molar ratio of polymerized units per TPV/polymerized units based on PAVE is preferably from 85/15 to 25/75, more preferably from 75/25 to 40/60.

As a particularly preferred specific examples of the fluorocarbon resin can be mentioned PTFE, TFE (40-60 mol.%/P (60-40 mol.%), the TFE (40 to 70 mol.%)/CF2=CFOCF3(60-30 mol.%), the TFE (40 to 70 mol.%)/CF2=CFOC3F7(60-30 mol.%), the TFE (40 to 70 mol.%)/CF2=C(OC2F5)2(60-30 mol.%), the TFE (70-30 mol.%)/PHE (30-70 mol.%), the TFE (70-30 mol.%)/AVE (30-70 mol.%), the TFE (70-30 mol.%)/BWA (30-70 mol.%), the TFE (60-30 mol.%)/AVE (1-69 mol.%)/BWA (1-69 mol.%), the copolymer WDF (40-70 mol.%)/CF2=CFOC3F7(60-30 mol.%), copolymer e (40-60 mol.%)/HFP (60-40 mol.%) or TFE (30 to 60 mol.%)/P (20-50 mol.%)/WDF (1-40 mol.%).

Here TFE (40-60 mol.%)/P (60-40 mol.%) means a copolymer obtained by copolymerization of TPV and P in the ratio of 40 to 60 mol.%:60-40 mol.%, and the same applies to the other copolymers.

The latex polymer of the present invention can be obtained by adding the emulsifier of the present invention to the latex polymer obtained by using another emulsifier to replace emulsifier or emulsion polymerization flarmanager, particularly preferably latex receive emulsion polymerization.

The latex polymer of the present invention containing fluorinated emulsifier, can be concentrated by various methods such as ED (this method is also mentioned as a method of electrodecantation or method electrodancetrance), sedimentation method centrifuger the cation or the method of heat sedimentation, as described in the manual of fluorinated resins "Fluororesin Handbook (p. 32, published in 1990 Nikkan Kogyo Shimbun, Ltd., edited by Takaomi Satokawa)".

The degree of concentration is such that the concentration of polymer in the latex polymer is preferably at least 30 wt.%, more preferably at least 40 wt.%, further preferably at least 50 wt.% and particularly preferably at least 60 wt.%. The upper limit of the concentration of the fluoropolymer is preferably at most 80 wt.%, particularly preferably at most 70 wt.%.

When the fluoropolymer is PTFE, the composition of the latex with a high concentration of PTFE, which is obtained has a concentration of PTFE from 30 to 70 wt.%, more preferably from 50 to 70 wt.%, particularly preferably from 55 to 70 wt.%.

While concentration is preferred to stabilize the latex by the addition of the emulsifier of the present invention or other hydrocarbon emulsifier. As the hydrocarbon emulsifier preferred anionic emulsifier or nonionic emulsifier, and more preferred nonionic emulsifier.

The latex of the polymer obtained according to the present invention, can be coagulated by known method to obtain a fluoropolymer. For coagulation can be applied by a method such as a method of vysalivaniya using m is a metallic salt or similar connection, the method of acid coagulation using an inorganic acid such as hydrochloric acid, the method of mechanical shear or the method of freezing and thawing.

When the polymer obtained by the method of the present invention has elastomeric properties, the crosslinking reaction can be performed by a known method. As a specific example of such a crosslinking reaction can be described crosslinking by peroxide crosslinking a polyol, a crosslinking an amine, stitching the triazine or similar reactions. Stitching peroxide is preferably used, keeping in mind performance, heat resistance and chemical resistance of different products that will be obtained by crosslinking the fluoropolymer composition, which is obtained by mixing the polymer with cross-linking reagent and other components of the reagents.

As cross-linking reagent used for stitching peroxide, it is preferable to apply an organic peroxide, which generates peroxy radicals when heated, etc. As a specific example of such a cross-linking reagent provides dialkylphenols, such as di-tert-butylperoxide, tert-butylcumylperoxide, dicumylperoxide, α,α-bis(tert-BUTYLPEROXY)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane or 2,5-dimethyl-2,5-di(tert-BUTYLPEROXY)hexane-3, 1,1-bis(tert-BUTYLPEROXY and)-3,3,5-trimethylcyclohexane, 2.5-dimethylhexane-2,5-dihydroxymonoxide, benzoyl peroxide, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxybenzoate acid or tert-butyl peroxy isopropyl carbonate. Especially preferred is dialkylphenols. Organic peroxide type that should be used, and its content in the composition of polymer (elastomer) is usually chosen on the basis of, for example, the activity of the organic peroxide or its temperature of decomposition.

The content of the organic peroxide is from 0.3 to 10 wt. parts to 100 wt. parts of the fluorine-containing elastomer. If the content is within this range will be obtained by a well-balanced properties of strength and elongation due to crosslinking. The interval is preferably from 0.3 to 5 wt. parts, particularly preferably from 0.5 to 3 wt. parts.

In the crosslinking composition obtained by mixing an organic peroxide with a fluorine-containing elastomer obtained by the method of the present invention may preferably be included cross-linking additive. When cross-linking additive is enabled, the generated radicals will effectively react with cross-linking additive to increase the efficiency of crosslinking. As such a crosslinking additive may be a compound which has the reaction ability of the Yu in relation to peroxide radicals and radicals in the molecules of fluorine-containing elastomer.

As a specific example of a cross-linking additive provides treelistener, triallylisocyanurate, trimethylsilane, triarylamine, triallylamine, N,N'-m-phenylenevinylene, p-financiacion, p,p'-dibenzoylhydrazine, dipropyleneglycol, diallylphthalate, N,N',N",N"'-Tetraethylenepentamine or siloxane oligomer containing vinyl groups, such as polymethylvinylsiloxane or polymethylvinylsiloxane, preferably treelistener, triallylisocyanurate or trimethylsilane, particularly preferably of triallylisocyanurate.

The content of the crosslinking additive is preferably from 0.1 to 10 wt. parts, more preferably from 0.5 to 5 wt. parts to 100 wt. parts of the fluorine-containing elastomer. If the content is within this range will be obtained by a well-balanced properties of strength and elongation due to crosslinking.

Further, the crosslinked composition, which is obtained from the fluorine-containing elastomer of the present invention, with the purpose of coloring compositions can be entered pigment, filler, reinforcing agent, etc. as a filler or reinforcing means, which are usually used contained carbon black, titanium oxide, silicon dioxide, clay, talc, polytetrafluoroethylene, vinylidenechloride, polivinilhlorid, polychlorotrifluoroethylene is, copolymer of a tetrafluoroethylene/ethylene, a copolymer of a tetrafluoroethylene/propylene or a copolymer of a tetrafluoroethylene/vinylidenefluoride.

Fluorine-containing emulsifier contained in the waste solution obtained in the coagulation of the latex polymer obtained by the method according to the present invention, can be regenerated in a known manner and recycled. As this method of regeneration may be the way its adsorption on a strongly basic anion-exchange resin or a weakly-basic anion-exchange resin, the method of its adsorption on the synthetic adsorbent, the method of adsorption on activated carbon, the method of its inclusion in the layered double hydroxide, the method of concentration wastewater, etc. Fluorinated emulsifier used in the present invention, which is recovered in the above manner, may be reproduced by any known method.

Now the present invention will be described in more detail with reference to Examples. However, the present invention is in any case not limited to.

Example 1

In a reactor operating under pressure, made of stainless steel, having an internal volume of 3200 cm3equipped with a stirrer, a load of 1500 g of deionized water, 40 g of disodium hydrogen phosphate of dodecahydrate, 0.5 g of sodium hydroxide, 198 g of tert-butanol, 8 g C4F9OCF2F 2OCF2COONH4(hereinafter referred to as BEA) and 2.5 g of ammonium persulfate. Next, introduce an aqueous solution containing 0.4 g of EDTA (disodium ethylenediaminetetraacetate dehydrate, he same applies hereinafter) and 0.3 g of ferrous sulphate heptahydrate iron, previously dissolved in 200 g of deionized water. Then gave TPV and P in a molar ratio of TPV/R=85/15, so as to bring the internal pressure of the reactor to 2.5 MPa (gauge pressure) at 25°C. the Stirrer was rotated at 300 rpm and was added 2.5 wt.% an aqueous solution of rongalite (sodium of hydroxymethanesulfinic dihydrate, the same applies hereinafter), to initiate the polymerization reaction.

With the initiation of polymerization, the inner pressure of the reactor is reduced by 0.01 MPa, and then pre-cooked mixed gas TPV/P=56/44 (molar ratio) was applied to increase the internal pressure of the reactor to of 2.51 MPa (gauge pressure). The polymerization reaction was continued by repeating this operation, and sequentially adding the mixed gas of TPV/R in order to maintain the internal pressure of the reactor in the range from 2.49 to of 2.51 MPa (gauge pressure). When the total amount added to the mixed gas has reached 800 g, adding an aqueous solution of rongalite stopped and then the internal temperature was lowered to 10°C to complete the reaction the s polymerization. Thus, the amount of aqueous solution of rongalite consumed by polymerization, was 30.0 g, and the polymerization time was about 5.5 hours. The above operation was obtained latex of the copolymer of TPV/R-containing BYA. Coagulated product formed during the emulsion polymerization, collected, dried in an oven at 120°C for 12 hours and weighed, its weight was 4,8,

The latex thus obtained, was added to 5% aqueous solution of calcium chloride to coagulate the latex by salting out with getting TFE/P. This copolymer was collected by filtration, washed with deionized water and dried in the oven and got 795 g white TFE/P.

The fluorine content in the polymer thus obtained was 58,2 wt.%, and the ratio of the copolymerization of TPV/R, calculated on the basis of such content, was 56,3/43,7 (molar ratio).

Example 2

In a reactor operating under pressure, made of stainless steel, having an internal volume of 2100 cm3equipped with a stirrer, was loaded with 1500 g of deionized water, 17 g of BEA and 300 g of PERFLUORO(propilenovomu ether) (hereinafter referred to as PPVE). While the mixture was stirred anchor agitator with a speed of 300 rpm, the internal temperature of the reactor was raised to 60°C. After the internal temperature reached 60°C, TF is filed so that to bring the internal pressure of the reactor to 1.0 MPa (gauge pressure). Then added 5 ml of 2.5 wt.% an aqueous solution of ammonium persulfate to initiate the polymerization reaction. As the progress of the polymerization, the internal pressure of the reactor was decreased to 0.01 MPa, and then fed TPV to increase the internal pressure of the reactor to 1.01 MPa (gauge pressure). The polymerization reaction was continued by repeating this operation, and sequentially adding the gas TPV to maintain the internal pressure of the reactor from 0.91 to 1.01 MPa (manometrical pressure).

Each time was added 15 g of gas TPV, the reactor was filed 15 ml of the previously prepared mixed solution of PVA/Ugva=98/2 (molar ratio). Adding the mixed solution was continued until the consumption of 105 g of TPV. The number of additions this mixed solution was only 7, which equals 105 ml. When the total number of added gas TPV reached 120 g, adding TPV stopped and then the internal temperature of the reactor was lowered to 10°C to complete the polymerization reaction. Curing time was about 4.5 hours. The above operation is obtained latex of TFE/PPVE/Ugva containing BYA. Coagulated product formed during the emulsion polymerization, collected, dried in an oven at 120°C for 12 hours and vesvese is Ali, his weight was 2.5,

The latex thus obtained, was added to 3.6 N aqueous solution of hydrochloric acid to coagulate it, adjusting the pH, with the receipt of TFE/PPVE/Ugva. This copolymer was collected by filtration, washed with ultrapure water, dried in the oven and got 380 g white TFE/PPVE/Ugva.

Copolymerization ratio of monomers TPV/PVE/Ugva in TFE/PPVE/Ugva, thus obtained, was TPV/PVE/Ugva=54/44/2 (molar ratio).

Example 3

100 l polymerization vessel was loaded 736 g of solid paraffin, 59 l of ultrapure water and 33 g of BEA. Then the mixture was heated to 70°C and purged with nitrogen, followed by deaeration. After this was introduced TPV to bring pressure to 1.9 MPa. When stirring was applied for 1 l of 0.5 wt.% an aqueous solution of peroxide dinternal acid to initiate polymerization. As the progress of the polymerization TPV was consumed, resulting in the pressure in the polymerization vessel was reduced. Accordingly, the TPV was continuously applied during the polymerization to maintain a constant pressure. After about 45 minutes from the initiation of polymerization, the temperature was raised to 90°C with a speed of 6°C/hour. Further, when the number of TPV reached 6.6 kg, was added 1 l of 5.6 wt.% aqueous solution of BYA. After 140 minutes from the initiation of polymerization, mixing and baking is the TPV stopped and TPV blew from the polymerization vessel, to complete the polymerization. The obtained latex of PTFE containing a 24.3 wt.% solids coagulate to separate PTFE in the wet state. Then the separated PTFE in the wet state were dried at 205°C with getting 6530 g of fine powder of PTFE. Coagulated product formed during the emulsion polymerization, collected, dried in an oven at 120°C for 12 hours and weighed, its weight was 63,2,

Example 4

793 g of the TFE/P was obtained in the same manner as in Example 1, except that n-C6F13OCF2CF2OCF2COONH4was used instead of BYA. Received 5,1 g coagulated product. The data shown in Table 1.

Example 5

374 g of TFE/PPVE/Ugva were obtained in the same manner as in Example 2, except that n-C6F13OCF2CF2OCF2COONH4was used instead of BYA. Obtained 3.2 g coagulated product. The data shown in Table 1.

Example 6

Latex PTFE containing 24,0 wt.% a solid substance was obtained in the same manner as in Example 3 except that n-C6F13OCF2CF2OCF2COONH4was used instead of BYA. Then 6523 g of fine powder of PTFE was obtained in the same manner as in Example 3. Received 68,6 g coagulated product. The data shown in the face 1.

Example 7

796 g of the TFE/P was obtained in the same manner as in Example 1, except that C4F9O(CF2CF2O)2CF2COONH4was used instead of BYA. Obtained 4.6 g coagulated product. The data shown in Table 1.

Example 8

378 g of TFE/PPVE/Ugva was obtained in the same manner as in Example 2, except that C4F9O(CF2CF2O)2CF2COONH4was used instead of BYA. Obtained 2.8 g coagulated product. The data shown in Table 1.

Example 9

Latex PTFE containing 24,1 wt.% a solid substance was obtained in the same manner as in Example 3, except that C4F9O(CF2CF2O)2CF2COONH4was used instead of BYA. Then 6532 g of fine powder of PTFE was obtained in the same manner as in Example 3. Received of 63.7 g coagulated product. The data shown in Table 1.

Example 10

Latex PTFE containing the emulsifier of the present invention and having a PTFE concentration of 25.3 wt.%, obtained as in Example 3, was added 5 wt.%, in the calculation of PTFE, polyoxyethyleneglycol ether. Then the mixture was concentrated by method of electrodancetrance obtaining 10,9 kg 60% latex of PTFE. Dry weight of coagulated product, formed at the time of this concentration, was 53 g, and it was 4.9 wt.% per received 60 wt.% the PTFE latex.

Comparative example 1

Latex copolymer TPV/R was obtained in the same way as in Example 1, except that perforateed ammonium (hereinafter referred to as PFOA) was used as emulsifier. An aqueous solution of rongalite consumed in the polymerization, was at 51.1, curing Time was 6.5 hours. Coagulated product was 8.9, Then latex coagulate and dried as in Example 1, obtaining 786 g of TFE/P. the Content of fluorine in such a fluoropolymer was to 57.9 wt.%, and copolymerization attitude TPV/R, calculated on the basis of this content, was 55,8/44,2 (molar ratio).

Comparative example 2

369 g of TFE/PPVE/Ugva was obtained as in Example 2, except that PFOA used as an emulsifier instead of BYA. The polymerization time was 5.5 hours. Coagulated product was 4.7, Then copolymerization attitude TPV/PVE/Ugva=59/39/2 (molar ratio).

Comparative example 3

Latex PTFE containing 23.5 wt.% a solid substance was obtained in the same manner as in Example 3, except that PFOA was used as the emulsifier instead of BYA. Then 6519 g of fine powder of PTFE was obtained in the same manner as in Example 3. Received 98,3 g is aguiriano product. The data shown in Table 1.

Comparative example 4

Latex PTFE containing PFOA and having a PTFE concentration of 24.8 wt.%, obtained as in Comparative example 3, was added 5 wt.%, in the calculation of PTFE, polyoxyethylene-octylphenols ether. Then the mixture was concentrated by method of electrodancetrance obtaining 10.8 kg 60 wt.% latex PTFE. Dry weight of coagulated product formed during the concentration was 83 g, and it was 7.7 wt.% per received 60% of the PTFE latex.

Performance fluoropolymer latex and stability of the fluoropolymer latex during storage in the Examples and Comparative examples were evaluated by the following method (see table 2).

(1) Performance fluoropolymer latex

Performance fluoropolymer latex was evaluated by the following standards.

High polymerization rate is faster than with a conventional emulsifier.

Secondary: the rate of polymerization equal to the speed with conventional emulsifier.

Low: the rate of polymerization is slower than with a conventional emulsifier.

(2) the stability of the latex of the polymer during storage

The resulting latex polymer was diluted with deionized water to bring the concentration of polymer to 30 wt.%. Then in a cylindrical glass container having a height of 10 cm and an internal volume of 100 m is, download latex was sealed and left to stand in a dark cool place for 1 month. And then the ratio of the transparent layer, which is the upper layer of the latex thus obtained upon standing, was calculated in percent. The smaller this value is, the higher the storage stability.

Table 1
The fluorinated emulsifier of the formula (1)Curing time (hour)Performance fluoropolymer latexThe stability of the latex of the polymer during storage
nmA
Example 141NH45,5high1
Example 241NH44,5high1
Example 3 41NH42,3high42
Example 461NH46,0high2
Example 561NH45,0high2
Example 661NH42,5high45
Example 742NH46,0high1
Example 842NH45,0high1
Example 942NH42,5high43

Table 2
EmulsifierCuring time (hour)Performance fluoropolymer latexThe stability of the latex of the polymer during storage
Comparative example 1PFOA6,5average5
Comparative example 2PFOA5,5average6
Comparative example 3PFOA2,7average73

Industrial application

The latex polymer of the present invention can be used to obtain a latex of a polymer such as silicone elastomer or formula. Latex is of terpolymer of the present invention can be used as a means for coating various materials, such as metal substrates, inorganic oxide substrates, polymer substrates, synthetic fiber, glass fiber, carbon fiber or natural fiber. Further, the fluoropolymer obtained by coagulation of the latex polymer is useful as a material excellent in heat resistance, oil resistance, chemical resistance, weather resistance, lipcote, antiobrastayuschim properties, hydrophobic properties, oil repellent properties, restoreselection properties, etc.

The entire contents of Japanese patent application No. 2004-220860, filed July 28, 2004, including the description, claims and abstract, is fully incorporated into the present application.

1. The latex polymer containing a fluorocarbon resin and a fluorinated emulsifier represented by the formula (I): F(CF2)4OCF2CF2OCF2COOA (where a is a hydrogen atom, alkali metal or NH4).

2. The latex polymer of claim 1, wherein the fluoropolymer is a copolymer of at least one formanager selected from the group consisting of tetrafluoroethylene, vinylidenefluoride, hexaferrite, CF2=C(ORf)nF2-n(where Rf- C1-8performanceline group or performanceeasy group containing at least one ether linkage in the molecule, n=1 or 2, and each carbon is EPA may be linear chain, may contain a branched chain or may have a cyclic structure) and chlorotrifluorethylene, if necessary, at least one monomer selected from the group consisting of CH2=CHOR (where R is C1-8an alkyl group or oxyalkylene group containing at least one ether bond, and any one of the carbon chains may be linear circuit may contain a branched chain or may have a cyclic structure), propylene and ethylene, and, if necessary, at most 10 mol.% the monomer containing a crosslinking group.

3. The latex polymer according to claim 1 or 2, in which the fluoropolymer is at least one member selected from the group consisting of a polymer of tetrafluoroethylene, a copolymer of a tetrafluoroethylene (from 40 to 60 mol.%)/propylene (60 to 40 mol.%) and a copolymer of a tetrafluoroethylene (from 40 to 70 mol.%)/CF2=FF3(from 60 to 30 mol.%), copolymer of a tetrafluoroethylene (from 40 to 70 mol.%)/CF2=F3F7(from 60 to 30 mol.%).

4. The way to obtain a latex of a polymer which comprises emulsion polymerization formanager in an aqueous medium containing from 0.001 to 10.0 wt.% fluorinated emulsifier represented by the formula (1): F(CF2)4OCF2CF2OCF2COOA (where a is a hydrogen atom, alkali metal or NH4), with fluoropolymer latex.

5. The way the floor is the treatment of the latex polymer according to claim 4, in which formname, which is at least one formononetin selected from the group consisting of tetrafluoroethylene, vinylidenefluoride, hexaferrite, CF2=C(ORf)nF2-n(where Rf- C1-8performanceline group or performanceeasy group containing at least one ether linkage in the molecule, n=1 or 2, and each carbon chain may be linear circuit may contain a branched chain or may have a cyclic structure), and chlorotrifluoroethylene will copolymerized, if necessary, at least one monomer selected from the group consisting of CH2=CHOR (R1-8an alkyl group or oxyalkylene group containing at least one ether bond, and any one of the carbon chains may be linear circuit may contain a branched chain or may have a cyclic structure), propylene and ethylene, and if necessary will copolymerized at most 10 mol.% the monomer containing a crosslinking group.

6. The latex polymer which is obtained by concentration of the latex polymer obtained by the method defined in claim 4 or 5, to the concentration of the fluoropolymer is at least 30 wt.%.

7. The fluorocarbon resin, which is obtained by coagulation of the latex polymer obtained by the method defined in claim 4 or 5.



 

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9 cl, 1 tbl, 1 dwg, 6 ex

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7 cl, 2 tbl, 6 ex

FIELD: chemistry.

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EFFECT: invention allows for obtaining a copolymer product with unique physical properties.

31 cl, 5 ex, 6 dwg

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