WO2006109740A1 - Agents perfluoroalkylants et procede de fabrication de polymeres organiques perfluoroalkyles - Google Patents

Agents perfluoroalkylants et procede de fabrication de polymeres organiques perfluoroalkyles Download PDF

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WO2006109740A1
WO2006109740A1 PCT/JP2006/307485 JP2006307485W WO2006109740A1 WO 2006109740 A1 WO2006109740 A1 WO 2006109740A1 JP 2006307485 W JP2006307485 W JP 2006307485W WO 2006109740 A1 WO2006109740 A1 WO 2006109740A1
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Prior art keywords
organic polymer
perfluoroalkyl
radical
containing organic
perfluoroalkylating agent
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PCT/JP2006/307485
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English (en)
Japanese (ja)
Inventor
Taizo Ono
Megumi Sato
Takahiro Kitahara
Tetsuo Shimizu
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National Institute Of Advanced Industrial Science And Technology
Daikin Industries, Ltd.
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Priority to JP2007512981A priority Critical patent/JPWO2006109740A1/ja
Publication of WO2006109740A1 publication Critical patent/WO2006109740A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring

Definitions

  • the present invention relates to a perfluoroalkylating agent and a method for producing a perfluoroalkylated organic polymer.
  • Rf 1 represents a perfluoroalkyl group having 1 to 10 carbon atoms
  • X 1 represents H, Cl, F or a methyl group
  • X 2 represents H, Cl, F or the like.
  • a method of heating after mixing with a resin such as polysalt bulbule (see, for example, Patent Document 2 and Patent Document 3).
  • the amount added in order to increase the surface modification effect, the amount added must be increased. In this case, the characteristics of the original resin itself may change.
  • Patent Document 1 Japanese Patent Laid-Open No. 62-235339
  • Patent Document 2 Japanese Patent Laid-Open No. 63-120789
  • Patent Document 3 Japanese Patent Laid-Open No. 4-223110
  • Patent Document 4 Japanese Patent Laid-Open No. 4-304243
  • Patent Document 5 Japanese Patent Laid-Open No. 5-214138
  • Non-Patent Document 1 J. Appl. Polym. Sci., 19, 1439 (1975)
  • Non-Patent Document 2 Journal of Industrial Chemistry, 73 (6), 1211 (1970)
  • an object of the present invention is a perfluorinated alkylation capable of easily and safely modifying a C ⁇ -containing organic polymer having a C ⁇ bond without using special equipment.
  • Another object of the present invention is to provide a method for producing a perfluoroalkyl organic polymer comprising the action of an agent and the perfluoroalkylating agent.
  • the present invention provides the above-mentioned C by acting on a C ⁇ -containing organic polymer having a C ⁇ bond.
  • a perfluoroalkylating agent for substituting ⁇ in the ⁇ bond with a perfluoroalkyl group which has the following general formula (I)
  • Ra represents a carbon atom having one unpaired electron
  • Y ⁇ ⁇ 2 and ⁇ 3 are the same or different and represent F or Rf
  • Rf is linear or branched.
  • the present invention provides a perfluoroalkyl group in which H in the CH bond is substituted with a perfluoroalkyl group by allowing the perfluoroalkyl encapsulant to act on a CH-containing organic polymer having a CH bond.
  • Perful consisting of producing an alkyloalkylated organic polymer In the method for producing a fluoroalkyl organic polymer, the above-mentioned perfluoroalkylating agent is used at a temperature higher than a temperature at which a very stable perfluoroalkyl radical is decomposed to generate a low molecular perfluoroalkyl radical.
  • a method for producing a perfluoroalkylated organic polymer which is carried out at a temperature.
  • the perfluoroalkylating agent of the present invention substitutes a perfluoroalkyl group for H in the C—H bond by acting on a CH-containing organic polymer having a CH bond.
  • the extremely stable perfluoroalkyl radical force represented by the general formula (I) is also obtained.
  • the C H -containing organic polymer is an organic polymer having a C H bond. It is sufficient that at least one CH bond is present in one molecule of the organic polymer having the CH bond.
  • CH-containing organic polymer examples include synthetic polymers, oligomers, cellulose, polysaccharides, and the like.
  • the “synthetic polymer” usually means a polymer having a degree of polymerization of about 100 or more, or a molecular weight of about 10,000 or more.
  • the term “oligomer” generally refers to those having a degree of polymerization of about 20 or more and less than about 100, or a molecular weight of about 2000 or more and less than about 10,000.
  • Examples of the synthetic polymer include CH-containing fluoropolymer having a CH bond, polyolefin, polyimide, polyphenylene sulfide, polyester, polycarbonate, polyamide, polyacetal, polyphenylene-oxide, polysulfone, polyphenol, urea resin, melamine resin.
  • Examples thereof include fat, alkyd resin, epoxy resin, polysiloxane, polyurethane, and the like.
  • C—H-containing fluoropolymer having a C—H bond, polyolefin, polyimide, polyphenylene sulfide, and polyester are preferable.
  • Examples of the C—H-containing fluoropolymer having a C—H bond include polyvinylidene fluoride [PVdF], ethylene Z tetrafluoroethylene copolymer [ETFE], and polyfluoride bur [PVF].
  • perfluoromonomers (1) such as tetrafluoroethylene [TFE], hexafluoropropylene [HFP], perfluorobulol ether [PAVE], and a trace amount of ethylene , Propylene, Fluoride Fluoride, Bilidene Fluora It may be a perfluoro copolymer obtained by polymerizing a CH-containing organic monomer (2) having a CH bond, such as an id.
  • Examples of the polyolefin include ethylene, propylene, butadiene, styrene, butyl chloride, salt vinylidene, (meth) acrylic acid, (meth) acrylic acid alkyl ester, tali-tolyl, and butyl acetate.
  • Examples of the homopolymer or copolymer include a polyethylene [PE], a polypropylene [PP], an acrylic polymer, a polybutyl alcohol, and a polybutyl butyral.
  • PE and PP strength S are preferable.
  • the PE may have a low density or a high density. However, the PE has a high density in that a perfluoroalkyl organic polymer having excellent properties such as mechanical strength can be obtained. I like things.
  • polyester examples include polyethylene terephthalate [PET] and polybutylene terephthalate [PBT].
  • H in the CH bond of the CH-containing organic polymer can be substituted with a perfluoroalkyl group by the action of the perfluoroalkylating agent of the present invention.
  • the perfluoroalkyl group is introduced by substituting the above-mentioned low molecular perfluoroalkyl radical force generated by the decomposition of the extremely stable perfluoroalkyl radical in the perfluoroalkylating agent of the present invention.
  • Examples of the perfluoroalkyl group include the kind of extremely stable perfluoroalkyl radical to be used, and the force depending on the reaction conditions on which the perfluoroalkylating agent of the present invention acts. For example, a trifluoromethyl group
  • the perfluoroalkyl group is preferably a trifluoromethyl group from the viewpoint of substitution reactivity.
  • the perfluoroalkylating agent of the present invention has the following general formula (I)
  • Y 1 Y 2 and Y 3 are the same or different and represent F or Rf, and the Rf is a linear or branched carbon number of 1 Represents ⁇ 16 perfluoroalkyl groups.
  • Rf is a linear or branched carbon number of 1 Represents ⁇ 16 perfluoroalkyl groups.
  • the Rf is not particularly limited as long as it is a perfluoroalkyl group having 1 to 16 carbon atoms, and may be linear or branched.
  • a perfluoroalkyl group having 1 to 3 carbon atoms is preferred, and a trifluoromethyl group is more preferred, because it easily generates a fluoroalkyl radical and is easily purified.
  • Ra is a carbon atom having one unpaired electron.
  • a carbon atom having one unpaired electron means a carbon having an unpaired electron of a radical on the atom.
  • Examples of the extremely stable perfluoroalkyl radical represented by the general formula (I) include the following general formula (la)
  • the above-mentioned extremely stable perfluoroalkyl radical is, in terms of easy preparation and substitution reactivity, extremely stable perfluoroalkyl radical (la), extremely stable perfluoroalkyl radical (lb), Stable perfluoroalkyl radicals (Ic) and extremely stable perfluoroalkyl radicals (Id) are preferred.
  • the extremely stable perfluoroalkyl radical (Id) is more preferable because the radical production is simple.
  • the extremely stable perfluoroalkyl radical (lb) is an alkyl compound obtained by binding, for example, the above low molecular perfluoroalkyl radical to the olefin obtained after decomposition to generate a low molecular perfluoroalkyl radical. It is more preferable in that it can be reused repeatedly by using a method of regenerating the above-mentioned extremely stable perfluoroalkyl radical by acting.
  • the recycling method is not particularly limited, but the method described in JP-A No. 003-147008 is preferable.
  • the extremely stable perfluoroalkyl radical preferably has 8 to 11 carbon atoms!
  • the more preferable lower limit of the carbon number is 9, and the more preferable upper limit of the carbon number is 10.
  • H in the C H bond can be easily substituted with a perfluoroalkyl group, which is preferable in that it can be implemented industrially at low cost.
  • the number of carbon atoms is 10, it is preferable in terms of easy reuse.
  • the carbon number of the extremely stable perfluoroalkyl radical is a concept including a carbon atom having one unpaired electron represented by Ra.
  • the extremely stable perfluoroalkyl radical is more preferably one that decomposes at 60 ° C or higher to generate a low-molecular perfluoroalkyl radical.
  • ultra-stable perfluoroalkyl radical decomposes at less than 60 ° C, it tends to be unstable and difficult to handle.
  • the above extremely stable perfluoroalkyl radicals include [(CF) CF] Ra-CF (CF)
  • Ra is the same as defined above
  • the extremely stable perfluoroalkyl radical can be produced by a known method.
  • [(CF) CF] Ra-CF (CF) by direct fluorination at a temperature of 0 to 45 ° C
  • the extremely stable perfluoroalkyl radical represented by the general formula (I) has a highly branched structure, and thus has a large steric hindrance. Therefore, it is usually at a temperature of less than 35 ° C. For example, it is easy to handle at room temperature of about 20-30 ° C.
  • the above extremely stable perfluoroalkyl radical can be easily decomposed by heating or the like to generate a low molecular weight perfluoroalkyl radical.
  • low molecular perfluoroalkyl radical refers to those having 1 to 16 carbon atoms derived from a part of the chemical structure of the above extremely stable perfluoroalkyl radical. It means radical.
  • a part of the chemical structure of the extremely stable perfluoroalkyl radical usually undergoes cleavage such as ⁇ -cleavage.
  • the low molecular weight perfluoroalkyl radical has a lower molecular weight than the extremely stable perfluoroalkyl radical!
  • the “low molecule” in the “low molecular perfluoroalkyl radical” means that the molecular weight is lower than that of the extremely stable perfluoroalkyl radical.
  • Examples of the low-molecular perfluoroalkyl radical include a trifluoromethyl radical, a pentafluoroethyl radical, a heptafluoropropyl radical, and the like.
  • the trifluoromethyl radical is preferred.
  • the above-described perfluoroalkylating agent of the present invention is applied to the above-described C C-containing organic polymer having a C ⁇ -bond.
  • ⁇ in the C—H bond, a perfluoroalkyl group is substituted.
  • the following perfluoroalkyl organic polymer is produced.
  • the C—H group-containing organic polymer is the same as that described in the description of the perfluoroalkylating agent of the present invention.
  • As the CH group-containing organic polymer a synthetic polymer is preferable.
  • the C—H group-containing organic polymer may be a single type or a composite of two or more types.
  • the above-mentioned perfluoroalkyl polymer in order to cause the above-mentioned perfluoroalkylating agent of the present invention to act, the above-mentioned perfluoroalkyl polymer is added to the above-mentioned CH-containing organic polymer.
  • the method for contacting the alkylating agent is not particularly limited.
  • the C—H-containing organic polymer can be brought into contact with the perfluoroalkylating agent as a composition having the C H-containing organic polymer power.
  • the composition comprising the CH-containing organic polymer is not particularly limited as long as it contains the CH-containing organic polymer.
  • a commercially available product depending on the type of the CH-containing organic polymer Ordinary supply forms such as powders and aqueous dispersions may be used as they are, or pellets obtained by melting and kneading or extruding the above powders into a kneader or extruder are used.
  • a molded product obtained by molding using the above supply form hereinafter referred to as “CH-containing organic polymer”. It may be referred to as a “molded body”.
  • the powder and the molded body may substantially contain only the CH-containing organic polymer.
  • the molded body made of the above-mentioned CH-containing organic polymer is not particularly limited, and examples thereof include molded articles, coatings, cast films, and the like.
  • the method and conditions of the molding process can be appropriately set by a known method according to the type of the molded body, the composition and amount of the C H -containing organic polymer to be molded, and the like.
  • the method for producing the molded product is not particularly limited, and examples thereof include compression molding, extrusion molding, paste extrusion molding, and injection molding.
  • the molded product can be formed into a desired shape such as a film, sheet, or block.
  • the method for forming the coating is not particularly limited, and examples thereof include spray coating and dip coating. Coating methods such as coating, brush coating, electrostatic coating, etc .; methods using impregnation and the like.
  • a method for producing the cast film for example, a coating film obtained by applying an aqueous dispersion made of a CH-containing organic polymer on a base material and then drying the base film can be obtained by, for example, putting it into water if desired. For example, a cast film formed by peeling off.
  • the C—H-containing organic polymer can be obtained only on the surface or the surface layer of the molded body by the action of the perfluoroalkylating agent.
  • the H possessed by the molecule can be replaced by a perfluoroalkyl group.
  • a perfluoroalkyl group is introduced only on the surface or surface layer of the molded product that also has the CH-containing organic polymer power, a perfluoroalkyl group is introduced into the molded product depending on the shape and thickness of the molded product.
  • the surface of the molded body has water repellency, oil repellency, chemical resistance, A characteristic that imparts characteristics such as non-adhesiveness and slidability, and also has the original properties of the CH-containing organic polymer strength under the surface, such as elasticity, toughness, rigidity, gas barrier properties, etc.
  • This complex can be obtained by a very simple method. Since the composite of the above characteristics has a continuity at the boundary between the surface or the surface layer portion having different characteristics and the inside as described above, compared to the molded body having organic polymer strength or the organic polymer itself, It can withstand long-term use without peeling at the boundary.
  • a molded body having different characteristics depending on the part for example, a composite molded body obtained by bonding two types of molded bodies having different characteristics prepared in advance, or a composite obtained by co-extrusion of two types of resin having different characteristics.
  • these conventional composite molded articles have a problem that they are easily peeled off at the boundary between two previously prepared parts having different characteristics.
  • the method of contacting the perfluoroalkylating agent with the composition comprising the CH-containing organic polymer differs depending on the shape, type, etc. of the composition comprising the CH-containing organic polymer.
  • a method comprising mixing the composition comprising the C—H-containing organic polymer and the perfluoroalkylating agent, the perfluoroalkylating agent, A method of contacting the composition containing the above-mentioned CH-containing organic high molecular force by circulating an alkylating agent can be used.
  • the molded product comprising the CH-containing organic polymer
  • a method of immersing the powder or pellet in the perfluoroalkylating agent, and the aqueous dispersion comprising the CH-containing organic polymer For example, a method of mixing the perfluoroalkylating agent with the perfluoroalkylating agent, a method of applying the perfluoroalkylating agent to the molded body made of the CH-containing organic polymer, or the like can be used.
  • the contact method is preferably an immersion method in terms of operability.
  • the perfluoroalkylating agent is brought into contact with the composition comprising a CH-containing organic polymer as described above. And act on the CH-containing organic polymer.
  • the action of the perfluoroalkylating agent is performed at a temperature (A) that is equal to or higher than the temperature at which the extremely stable perfluoroalkyl radical is decomposed to generate a low-molecular perfluoroalkyl radical. .
  • the above ⁇ temperature above the temperature at which the extremely stable perfluoroalkyl radical decomposes to generate a low molecular perfluoroalkyl radical (A) '' varies depending on the type of the perfluoroalkylating agent used. Although not particularly limited, 60 ° C or higher is preferable in that low-molecular perfluoroalkyl radicals that are preferably at or below the temperature are liable to be generated without causing thermal denaturation in the CH-containing organic polymer to be contacted. 80 ° C or more is more preferable.
  • the above temperature (A) is 130 ° C or lower when the C—H-containing organic polymer to be contacted is polyethylene, 180 ° C or lower when it is polypropylene, 255 ° C or lower when it is PET, and polyimide In some cases, each prefers below 400 ° C.
  • the low-molecular perfluoroalkyl radical is the same as that described in the above description of the perfluoroalkylating agent of the present invention, such as a trifluoromethyl radical.
  • Examples of the low molecular perfluoroalkyl radical include those exemplified above.
  • the perfluoroalkylating agent of the present invention described above is regenerated by the method described in JP-A-2003-147008, It may be reused repeatedly.
  • perfluoro-2,4 dialkyl is used.
  • perfluoro-2,4 dialkyl is used.
  • the perfluoroolefin after the release of the low-molecular perfluoroalkyl radical is reacted with trialkylperfluoroalkyl silane, and further fluorinated to produce perfluoro-3 ethyl 2- , 4-Dimethyl-1-pentyl can be reused.
  • the perfluoroalkylated organic polymer production method of the present invention can be performed under the reaction conditions according to the type of the C—H-containing organic polymer used in addition to the above reaction conditions.
  • the reaction is preferably performed in an inert gas atmosphere such as nitrogen so that side reactions do not occur.
  • various additives such as a diluent may be added as needed when the perfluoroalkylating agent is allowed to act.
  • the various additives are not particularly limited as long as they do not inhibit the substitution reaction of the CH group.
  • the time for which the above-mentioned perfluoroalkylating agent of the present invention is allowed to act is the CH group-containing organic polymer used or the perfluoroalkyl used. Different power depending on the type and amount of the alkyloalkylating agent From the viewpoint of productivity, it is preferably 1 to 72 hours.
  • a more preferable lower limit of the above time is 3 hours, and a more preferable upper limit of the above time is 50 hours.
  • the method for producing a perfluoroalkylated organic polymer of the present invention is a method for producing a perfluoroalkylated organic polymer.
  • the "perfluoroalkylated organic polymer” refers to the substitution of H in the CH bond of the above-described C—H-containing organic polymer with a perfluoroalkyl group. It is an organic polymer.
  • the perfluoroalkyl organic polymer is an organic polymer obtained by allowing the above-described perfluoroalkylating agent of the present invention to act on the C—H-containing organic polymer.
  • the perfluoroalkyl group is the perfluoroalkyl group described above with respect to the perfluoroalkylating agent of the present invention, that is, generated by decomposing the extremely stable perfluoroalkyl radical in the perfluoroalkylating agent.
  • the low molecular perfluoroalkyl radical is introduced by substituting the above H.
  • the perfluoroalkyl group include those described in the above description of the perfluoroalkylating agent of the present invention, such as a trifluoromethyl group.
  • the perfluoroalkyl group has a different force depending on the type of the perfluoroalkylated organic polymer to be obtained.
  • the FZC value power of the perfluoroalkylated organic polymer is 0.2 or more, 2. It is preferable to be present in the perfluoroalkylic organic polymer in an amount of 4 or less.
  • the perfluoroalkyl group is present in the HDPE molecule in an amount that gives an FZC value 0.2 to 0.6 for HDPE. sell.
  • the perfluoroalkylated organic polymer obtained by the method for producing a perfluoroalkylated organic polymer of the present invention is a powder, aqueous dispersion depending on the form of the above-mentioned composition containing C—H-containing organic polymer. It can be obtained as existing in the body, pellets, molded bodies and the like.
  • the extremely stable perfluoroalkyl radical used in the method for producing a perfluoroalkylated organic polymer of the present invention is as follows. While stable at room temperature and excellent in handleability, it can be easily decomposed by heating or the like to generate low-molecular perfluoroalkyl radicals. In addition, since the low molecular perfluoroalkyl radical acts on the above-described C H -containing organic polymer, it can be substituted with H in the C—H group.
  • the method for producing a perfluoroalkylated organic polymer of the present invention is as follows: (1) The above-mentioned perfluoroalkylating agent of the present invention easily generates the above low-molecular perfluoroalkyl radical at a certain temperature or higher. And (2) that the low molecular perfluoroalkyl radical acts on the above-mentioned CH-containing organic polymer, and that H in the C—H bond can be substituted with a perfluoroalkyl group. It is used to produce perfluoroalkylated organic polymers.
  • the above-mentioned perfluoroalkylating agent of the present invention is acted on the above-mentioned CH-containing organic polymer having a CH bond. It does not require a special device, for example, that is required when fluorine gas is allowed to act, and can be easily carried out without using a catalyst such as peroxide. Therefore, compared to conventional fluorination methods such as plasma treatment and treatment with hexafluoroacetone, the production cost and safety viewpoint are also preferred.
  • the perfluoroalkylated organic polymer obtained by the method for producing a perfluoroalkylated organic polymer of the present invention has a perfluoroalkyl group as described above, it is water- and oil-repellent and non-adhesive. Excellent in lubricity, chemical resistance, weather resistance, etc.
  • the critical surface tension of the perfluoroalkyl organic polymer varies depending on the CH-containing organic polymer used and is usually 15 to 50 dyneZcm.
  • the value of the critical surface tension is preferably as low as possible since many perfluoroalkyl groups are introduced.
  • the preferable upper limit of the critical surface tension is 30 dynes / cm.
  • the “critical surface tension” is calculated from a Zisman plot by measuring the contact angle ⁇ at 23 ° C. using a contact angle measuring device.
  • the perfluoroalkyl organic polymer of the present invention is produced. What was obtained by the method may be used as it is, or a secondary force such as cutting may be performed.
  • the above-mentioned perfluoroalkyl organic polymer is a CH group-containing organic polymer composition, which is the above-mentioned powder or aqueous dispersion, for example, a molded product, paint, coating, cast film, etc. Can be used for various purposes.
  • the perfluoroalkylating agent of the present invention has the above-described structure, it does not require a special device or the like! In a CH group-containing organic polymer by a simple method such as heating. H in the CH group can be replaced with a perfluoroalkyl group. Since the perfluoroalkylated organic polymer production method of the present invention uses the above-mentioned perfluoroalkylating agent of the present invention, it is possible to produce a perfluoroalkylated organic polymer simply and safely.
  • the resulting perfluoroalkylated organic polymer is perfluoroal Due to the effect of the kill group, it can be suitably used for producing a molded article excellent in water / oil repellency, non-adhesiveness, lubricity, chemical resistance, weather resistance and the like.
  • Tensile test evaluation device (trade name: Tensilon Universal Testing Machine RTC-1225A, manufactured by Orientec Co., Ltd.) was used for measurement under the conditions based on ASTM D-1708. The measurement temperature was 23 ° C and the test speed was 50 mmZmin.
  • Reagent A used in each example was perfluoro-3-ethyl-2,4-dimethyl-3-pentyl (57.6% by mass; where "% by mass” is the total mass of reagent A .. made of 3 Echiru -2 4- dimethyl pentane (24.2 mass 0/0) - ratio hereinafter the same), hexa full O b propylene trimer (17.8 wt%) and Pafuru O b to Is.
  • a high-pressure polyethylene [HDPE] press sheet (2cm x 2cm, thickness: 2mm) prepared by compression molding as a base material is placed in a 100ml stainless steel pressure-resistant container, and 6.5g of reagent A is placed in a sealed state. Thereafter, the gas in the vessel was replaced with nitrogen, and the oxygen concentration in the reaction system was set to 6 ppm.
  • the stainless steel pressure vessel was heated in an electric furnace at 85 ° C. for 24 hours. The container force was taken out, the surface reagent was wiped off, air-dried for 60 minutes, the FZC value was calculated by ESCA, the contact angle was measured, and the critical surface tension was calculated.
  • a sample was prepared in the same manner as described above except that a tensile test specimen prepared from an HDPE press sheet (thickness: 2 mm) was used as the substrate. The obtained samples were measured for tensile strength and evaluated for mechanical properties. [0058]
  • Example 2 a tensile test specimen prepared from an HDPE press sheet (thickness: 2 mm) was used as the substrate. The obtained samples were measured for tensile strength and evaluated for mechanical properties.
  • Example 2 A sample was prepared in the same manner as in Example 1 except that a HDPE film (2 cm ⁇ 2 cm, thickness: 0.2 mm) was used as the substrate, and the FZC value and critical surface tension were measured.
  • a test piece for a tensile test was prepared from an HDPE press sheet (thickness: 0.2 mm) in the same manner as in Example 1, and mechanical characteristics were evaluated.
  • PET film (2cm X 2cm, thickness: 0.25mm; product name: Lumirror, Torayen clay) as a base material into a stainless steel pressure vessel with a capacity of 100ml, and put reagent A5. 4g After sealing, the gas in the container was replaced with nitrogen, and the oxygen concentration in the reaction system was 6 ppm. The stainless steel pressure vessel was heated in an electric furnace at 85 ° C for 48 hours. A sample was taken from the container cover, wiped off the surface reagent, air-dried for 60 minutes, FZC value was calculated by ESCA, contact angle was measured, and critical surface tension was calculated.
  • PET polyethylene terephthalate
  • Comparative Example 3 Except that the heating temperature was set to 50 ° C, heating was performed in the same manner as in Example 1, a sample was prepared, the FZC value was calculated, the contact angle was measured, and the critical surface tension was calculated.
  • Table 1 shows the results regarding ESCA and FZC values
  • Table 2 shows the results regarding mechanical properties.
  • Example 3 PI film 0. 025 2. 0 X 2. 0 HFP trimer (17.8 mass 0/0) 5. 3 85 ° C 48hr 0. 42 27. 4 Compound 2 (24.2 wt%) Compound 1 (57.6 mass%)
  • the samples obtained in Examples 1 to 4 have a lower critical surface tension than the base material before treatment in Reference Examples 1 to 4, so that they are difficult to adhere to, that is, excellent in water repellency. I understood.
  • Example 1 The sample obtained in Example 1 has a larger FZC value than the sample obtained in Comparative Example 3, and the critical surface tension is small. Therefore, the temperature at which the C9 radical acts is low, and a low molecular perfluoroalkyl radical is generated. It was divided that it was effective when the temperature was higher.
  • the perfluoroalkylating agent of the present invention does not require a special apparatus or the like!
  • H in the CH group can be replaced with a perfluoroalkyl group.
  • the perfluoroalkylated organic polymer production method of the present invention uses the above-mentioned perfluoroalkylating agent of the present invention, a perfluoroalkylated organic polymer can be obtained easily and safely.
  • the resulting perfluoroalkylated organic polymer is capable of producing molded articles with excellent water and oil repellency, non-adhesiveness, lubricity, chemical resistance, weather resistance, etc. due to the effect of perfluoroalkyl groups. Can be suitably used.

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Abstract

Agents perfluoroalkylants capables de modifier des polymères organiques contenant des liaisons C-H, de manière simple, facile et sans danger sans installations spéciales ; et procédé de fabrication de polymères organiques perfluoroalkylés par action de l’agent perfluoroalkylant sur les polymères organiques contenant des liaisons C-H. L’invention concerne un agent perfluoroalkylant pouvant agir sur un polymère organique contenant des liaisons C-H et remplacer l’hydrogène (H) de la liaison C-H du polymère organique par un perfluoroalkyle, caractérisé en ce qu’il consiste en un radical libre perfluoroalkyle extrêmement stable, représenté par la formule générale (I) : [(CF3)2CF][(CF3)CY1Y2]Ra-CF(CF3)Y3 (I) où Ra est un atome de carbone ayant un électron non apparié ; Y1, Y2 et Y3 sont identiques ou différents et chacun soit F, soit Rf ; et Rf est un perfluoroalkyle linéaire ou ramifié ayant de 1 à 16 atomes de carbone.
PCT/JP2006/307485 2005-04-07 2006-04-07 Agents perfluoroalkylants et procede de fabrication de polymeres organiques perfluoroalkyles WO2006109740A1 (fr)

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JP2010031181A (ja) * 2008-07-30 2010-02-12 Mitsubishi Materials Corp 表面処理樹脂組成物の製造方法
JP2020111522A (ja) * 2019-01-09 2020-07-27 三菱マテリアル電子化成株式会社 易分解性安定パーフルオロアルキルラジカルの製造方法及びその易分解性安定パーフルオロアルキルラジカル試薬

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JPH05214138A (ja) * 1992-02-04 1993-08-24 Central Glass Co Ltd フッ素含有表面を有する成形品
JP2003147008A (ja) * 2001-11-16 2003-05-21 National Institute Of Advanced Industrial & Technology 低分子ラジカル供給方法、ラジカル運搬分子、重合体製造方法及び重合体
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JP2010031181A (ja) * 2008-07-30 2010-02-12 Mitsubishi Materials Corp 表面処理樹脂組成物の製造方法
JP2020111522A (ja) * 2019-01-09 2020-07-27 三菱マテリアル電子化成株式会社 易分解性安定パーフルオロアルキルラジカルの製造方法及びその易分解性安定パーフルオロアルキルラジカル試薬
JP7284583B2 (ja) 2019-01-09 2023-05-31 三菱マテリアル電子化成株式会社 パーフルオロアルキルラジカルの製造方法

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