WO2011043246A1 - 新規なフッ化ビニリデン共重合体及びその製造方法 - Google Patents
新規なフッ化ビニリデン共重合体及びその製造方法 Download PDFInfo
- Publication number
- WO2011043246A1 WO2011043246A1 PCT/JP2010/067154 JP2010067154W WO2011043246A1 WO 2011043246 A1 WO2011043246 A1 WO 2011043246A1 JP 2010067154 W JP2010067154 W JP 2010067154W WO 2011043246 A1 WO2011043246 A1 WO 2011043246A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinylidene fluoride
- mol
- fluoride copolymer
- polymerization
- formula
- Prior art date
Links
Images
Classifications
-
- 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
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
-
- 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
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/20—Vinyl fluoride
- C08F214/205—Vinyl fluoride with non-fluorinated comonomers
-
- 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
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- 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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
Definitions
- the present invention is a vinylidene fluoride copolymer having excellent heat resistance, weather resistance, chemical resistance, and stain resistance, good adhesion, and reduced coloration during molding processing, and the vinylidene fluoride copolymer It relates to a manufacturing method.
- the vinylidene fluoride copolymer obtained in the present invention is useful in the fields of various molded products, binders, paints and the like.
- Polyvinylidene fluoride resin composed of vinylidene fluoride units is excellent in chemical resistance, weather resistance, stain resistance and the like, and is used as a material for producing various films and molded products by melt molding. Moreover, although it is utilized also as a coating material or a binder, since polyvinylidene fluoride resin has low adhesive strength with base materials, such as a metal, improvement of adhesive strength is desired.
- VDF vinylidene fluoride
- copolymers of vinylidene fluoride As copolymers of vinylidene fluoride, copolymers with fluorine-containing monomers such as hexafluoropropylene and chlorotrifluoroethylene are known and commercialized (edited by Takaomi Satokawa, “Fluorine Resin Handbook”, first edition, Nikkan Kogyo Shimbun, November 30, 1990, p.363 (Non-Patent Document 2), etc.], however, these are not necessarily aimed at improving adhesiveness, and therefore, improvement in adhesiveness is still desired. It was rare.
- Patent Document 1 discloses that polyvinylidene fluoride is used as an adhesive or the like by graft polymerization of an acrylic monomer onto a skeleton of polyvinylidene fluoride irradiated with ionizing radiation. It shows how to treat it so that it can be adhered directly to the surface of the metal without an intermediary. However, since this method performs ionizing irradiation of radiation, it requires a large-scale facility.
- Patent Document 2 in a copolymer of vinylidene fluoride 40 to 95 mol% and maleic anhydride 5 to 60 mol%, the acid anhydride portion is 90% using alcohol or water. It has been shown that ⁇ 100% ring opening improves the solvent solubility and crosslinkability of the copolymer.
- Patent Document 3 discloses that 100 parts by weight of a monomer containing 80% by weight or more of vinylidene fluoride and unsaturated diesters such as maleic acid monomethyl ester and maleic acid monoethyl ester.
- a vinylidene fluoride copolymer obtained by copolymerizing 0.1 to 3 parts by weight of a monoester of a basic acid with improved adhesion to metals and the like and excellent in chemical resistance is shown.
- vinylidene fluoride copolymers having these esters or modified products thereof have difficulty in heat resistance, and in melt molding, there is a problem that the molded product is colored to reduce the commercial value. Improvement of sex was expected.
- JP 56-133309 (UK Patent Application Publication No. 20722203) Japanese Patent Laid-Open No. 2-604 Japanese Laid-Open Patent Publication No. 6-172452 (US Pat. No. 5,415,958)
- the main objects of the present invention are a vinylidene fluoride copolymer having excellent heat resistance, weather resistance, chemical resistance, stain resistance, good adhesion, and reduced coloration during molding, and the vinylidene fluoride It is providing the manufacturing method of a copolymer.
- the present inventors have found that a novel vinylidene fluoride having a specific proportion of vinylidene fluoride monomer units and methylidene malonate monomer units. It has been found that the copolymer can solve the problem. Further, by hydrolyzing and modifying the ester portion of the vinylidene fluoride copolymer, a vinylidene fluoride copolymer having a modified ester portion can be obtained, and the modified vinylidene fluoride copolymer is obtained. However, it was found that the problem can be solved.
- the vinylidene fluoride monomer unit represented by the formula (1) is 99.9 to 90 mol%
- the methylidene malonate ester monomer unit represented by the formula (2) is 0.1 to
- a vinylidene fluoride copolymer having a weight average molecular weight of 200,000 or more and having 10 mol% and 0 to 10 mol% of monomer units other than the monomer units is provided.
- R 1 and R 2 are each independently H or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, except when R 1 and R 2 are H at the same time.
- the vinylidene fluoride copolymer 10 to 90% of the total number of ester groups of the methylidene malonate monomer unit represented by the formula (2) is hydrolyzed.
- a modified vinylidene fluoride copolymer is provided.
- R 1 and R 2 are each independently H or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, except when R 1 and R 2 are H at the same time.
- a methylidene malonic acid ester represented by the above formula (2) is further used using an alkali metal halide or an alkali metal hydroxide.
- a method for producing a modified vinylidene fluoride copolymer which hydrolyzes 10 to 90% of the total number of ester groups contained in the monomer unit.
- the vinylidene fluoride copolymer of the present invention provides a vinylidene fluoride copolymer having excellent heat resistance, weather resistance, chemical resistance and stain resistance, good adhesion, and reduced coloring during molding. This is an effect.
- the ester group derived from methylidene malonate used as a comonomer with vinylidene fluoride is a chemically reactive functional group
- the vinylidene fluoride copolymer of the present invention has an ester moiety.
- chemical modification by reaction with various compounds is possible, and the desired functional group can be introduced into the vinylidene fluoride copolymer.
- the vinylidene fluoride copolymer of the present invention has an effect that it can be easily produced by aqueous suspension polymerization.
- the novel vinylidene fluoride copolymer of the present invention has a vinylidene fluoride monomer unit represented by the formula (1) of 99.9 to 90 mol%, represented by the formula (2).
- the vinylidene fluoride copolymer of the present invention preferably has 99.9 to 92 mol% of vinylidene fluoride monomer units and 0.1 to 8 mol% of methylidene malonate monomer units, and more Preferably, 99.8 to 94 mol% of vinylidene fluoride monomer units and 0.2 to 6 mol% of methylidene malonate monomer units, more preferably 99.8 to 96 mol of vinylidene fluoride monomer units.
- the vinylidene fluoride copolymer of the present invention has 99.9 to 90 mol% of the vinylidene fluoride monomer unit and 0.1 to 10 mol% of the methylidene malonate monomer unit. If necessary, it may have 0 to 10 mol% of monomer units other than these monomer units (sometimes referred to as “other monomer units”). In addition, these ratios are ratios calculated with the total of vinylidene fluoride monomer units, methylidene malonate ester monomer units, and other monomer units being 100 mol%.
- the proportion of other monomer units is 0 to 10 mol%, preferably 0.1 to 7 mol%, more preferably 0.3 to 5 mol%, particularly preferably 0.5 to 3 mol%. It is.
- the ratio of the other monomer units is less than 0.1 mol%, the same physical properties as those of the vinylidene fluoride copolymer consisting only of vinylidene fluoride monomer units and methylidene malonate monomer units And has characteristics, and there is almost no effect of incorporating other monomer units.
- the proportion of other monomer units exceeds 10 mol%, the intended physical properties and characteristics of the vinylidene fluoride copolymer of the present invention may be impaired.
- the weight average molecular weight of the vinylidene fluoride copolymer of the present invention is 200,000 or more, preferably 250,000 or more, more preferably 260,000 or more, and particularly preferably 270,000 or more. . If the weight average molecular weight is less than 200,000, sufficient mechanical strength may not be obtained.
- the upper limit of the weight average molecular weight of the vinylidene fluoride copolymer is not particularly limited, but is about 600,000, and usually about 500,000. When the weight average molecular weight exceeds 600,000, the moldability may be deteriorated, or the solubility in a solvent may not be sufficient in applications where it is used as a solution, and the polymerization time is significantly prolonged to increase productivity. descend.
- the number average molecular weight Mn of the vinylidene fluoride copolymer of the present invention is usually 90,000 to 300,000, preferably 100,000 to 250,000, more preferably 110,000 to 200,000.
- the number average molecular weight is less than 90,000, sufficient mechanical strength may not be obtained, and when the number average molecular weight exceeds 300,000, the moldability is deteriorated or the solvent is used for a use as a solution. In some cases, the solubility of is not sufficient, and the polymerization time is remarkably prolonged and productivity is lowered.
- the Mw / Mn representing the molecular weight distribution of the vinylidene fluoride copolymer of the present invention is usually 1.80 to 3.50, preferably 2.00 to 3.00, more preferably 2.10 to 2.50. is there.
- Mw / Mn exceeds 3.50, there is an adverse effect on the performance and moldability of molded products, and when Mw / Mn is less than 1.80, selection of molding processing conditions becomes difficult, Large spherulites may be generated during cooling.
- the inherent viscosity of the vinylidene fluoride copolymer of the present invention is usually 0.8-3. 8 dl / g.
- the inherent viscosity is less than 0.8 dl / g, sufficient mechanical strength may not be obtained.
- the inherent viscosity exceeds 3.8 dl / g, the moldability is deteriorated or used as a solution. In such a case, the solubility in a solvent may be reduced, and the polymerization time may be significantly prolonged to lower the productivity.
- the inherent viscosity varies depending on the intended use of the vinylidene fluoride copolymer. For example, it is preferably 0.8 to 1.8 dl / g, more preferably 0 for ordinary injection molding or extrusion molding. It is about 0.9 to 1.7 dl / g, particularly preferably about 0.95 to 1.5 dl / g. In the case of a fiber product such as a fishing line, it is preferably 0.9 to 3.8 dl / g, more preferably 1.0 to 3.7 dl / g, and particularly preferably about 1.1 to 3.5 dl / g.
- the vinylidene fluoride copolymer of the present invention comprises a vinylidene fluoride monomer unit of the formula (1), a methylidene malonate monomer unit of the formula (2), and other monomer units as necessary. It is what you have.
- the monomer forming the vinylidene fluoride monomer unit of the formula (1) is vinylidene fluoride, and the monomer forming the methylidene malonate monomer unit of the formula (2) is represented by the formula ( It is a methylidene malonate represented by 3).
- the monomer that forms the other monomer unit that the vinylidene fluoride copolymer of the present invention may have as necessary is a fluorine-containing monomer other than vinylidene fluoride, or a hydrocarbon such as ethylene or propylene.
- Monomer that is copolymerizable with vinylidene fluoride or methylidene malonate such as a monomer (hereinafter, also referred to as “copolymerizable monomer”), and preferred monomers are: It is a fluorine-containing monomer other than vinylidene fluoride. Specific examples include vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether.
- the vinylidene fluoride copolymer of the present invention is a random copolymer, a block copolymer, and a graft polymer, and any effects can be obtained as long as they exhibit characteristics and characteristics in accordance with the object of the present invention.
- a random copolymer is preferable because it is easy to produce.
- the monomer forming the methylidenemalonic acid ester monomer unit of the formula (2) is a methylidenemalonic acid ester represented by the formula (3).
- R 1 and R 2 are each independently H or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and include a diester and a monoester of methylidene malonic acid. When R 1 and R 2 are H at the same time, they are not included in the category of methylidene malonic acid ester represented by the formula (3).
- R 1 and R 2 a methyl group, an ethyl group, and a propyl group are preferable because a polymer can be obtained in a short time with good stability.
- R 1 or R 2 is an aliphatic hydrocarbon group having 6 or more carbon atoms
- the ester portion becomes bulky, and as a result, addition of a vinylidene fluoride radical or the like to the methylidene malonate is inhibited.
- the polymerization time is prolonged, or no addition to the methylidene malonic acid ester occurs, the polymerization proceeds only with vinylidene fluoride, and a vinylidene fluoride homopolymer is obtained.
- the effect of the present invention can be obtained not only by methylidene malonate but also by other alkylidene malonate such as ethylidene malonate and propylidene malonate.
- the methylidene malonate represented by the formula (3) can be obtained by a production method known per se.
- “A Versatile and Convenient Multigram Synthesis of Methylidenemalonic Acid Diesters” (“Widely applicable and useful multigram synthesis of methylidenemalonic acid diesters"): De Keyser, JL .; De Cock, C. J C .; Poupaert, J. H .; Dumont, P., J. Org. Chem., 1988, 53, p. 4859-4862), and dimethylidenemalonate dimethyl was synthesized according to the scheme of FIG.
- the vinylidene fluoride copolymer of the present invention contains at least 99.9 to 90 mol% of vinylidene fluoride and 0.1 to 10 mol of methylidene malonate represented by the formula (3). % And a monomer mixture containing 0 to 10 mol% of a copolymerizable monomer, and a polymerization initiator are dispersed in an aqueous medium containing a dispersion stabilizer, and a polymerization reaction is performed. be able to.
- the polymerization reaction can be carried out by suspension polymerization or emulsion polymerization, but suspension polymerization is preferred from the viewpoint of easy recovery of the vinylidene fluoride copolymer.
- the monomer mixture contains at least 99.9 to 90 mol% of vinylidene fluoride, 0.1 to 10 mol% of methylidene malonate represented by the formula (3), and copolymerization A monomer mixture containing 0 to 10 mol% of possible monomers.
- the proportion of vinylidene fluoride and methylidene malonate in the monomer mixture is 99.9 to 90 mol% of vinylidene fluoride and 0.1 to 10 mol% of methylidene malonate, preferably vinylidene fluoride.
- the proportion of the copolymerizable monomer is within a range that does not adversely affect the heat resistance, weather resistance, chemical resistance, stain resistance, adhesion, moldability, mechanical properties, etc., and the polymerization reaction.
- a monomer mixture comprising vinylidene fluoride, a methylidene malonate represented by the formula (3), and a copolymerizable monomer, preferably 0.1 to 7
- the mol% more preferably 0.3 to 5 mol%, particularly preferably 0.5 to 3 mol%.
- ratios are ratios calculated with the total of vinylidene fluoride monomer units, methylidene malonate ester monomer units, and other monomer units as 100 mol%, and vinylidene fluoride,
- the optimum range may be selected in consideration of the polymerization reactivity of the methylidene malonic acid ester and the copolymerizable monomer.
- the amount of the polymerization initiator used is preferably as small as possible in order to obtain a vinylidene fluoride copolymer having good thermal stability.
- the range is preferably 0.01 to 2% by mass, more preferably 0.05 to 1.5% by mass, and still more preferably 0.1 to 1.2% by mass.
- the polymerization initiator exceeds 2% by mass, it becomes difficult to use it effectively in the polymerization reaction, and the resulting polymer tends to deteriorate in high-temperature coloring resistance and elution.
- Dispersion stabilizer when performing emulsion polymerization as a polymerization reaction, a general-purpose fluorine emulsifier can be used.
- a suspending agent used in usual suspension polymerization can be used, such as partially saponified polyvinyl acetate, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, etc.
- Water-soluble polymers such as water-soluble cellulose ethers, acrylic acid polymers, and gelatin can be exemplified.
- the amount of the suspending agent is usually 0.01 to 2% by weight, preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the amount of the monomer mixture. Used in
- Aqueous medium As the aqueous medium, ordinary ion-exchanged water, distilled water, ultrapure water, or the like can be used.
- the amount of the aqueous medium used is such that the ratio (mass ratio) of the aqueous medium / monomer mixture is usually 1/1 to 10/1, preferably 1.5 / 1 to 8/1, more preferably 2 /. It is in the range of 1 to 6/1, particularly preferably 2.5 / 1 to 5/1.
- the ratio of the aqueous medium / monomer mixture is less than 1/1, stirring, heat removal, and particle size control become difficult. Further, when the ratio exceeds 10/1, there is a problem that the production efficiency is lowered.
- a small amount of a halogenated hydrocarbon solvent may be used in combination.
- a halogenated hydrocarbon solvent for example, monohydropentafluorodichloropropane, especially 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane or When these mixtures are used in combination, the amount of the polymerization initiator used can be reduced.
- These halogenated hydrocarbon solvents can be used in an amount of 10 to 50 parts by weight, preferably 15 to 40 parts by weight, based on 100 parts by weight of the aqueous medium.
- Chain transfer agents include acetone, isopropyl acetate, ethyl acetate, diethyl carbonate, dimethyl carbonate, pyrogenic ethyl carbonate, propionic acid, trifluoroacetic acid, trifluoroethyl alcohol, formaldehyde dimethyl acetal, 1,3-butadiene epoxide, 1,4 -Dioxane, ⁇ -butyl lactone, ethylene carbonate, vinylene carbonate, etc. are mentioned, but it effectively reduces the molecular weight or inherent viscosity and does not hinder the thermal stability of the vinylidene fluoride copolymer, and is easily available.
- the amount of the chain transfer agent used is 0.05 to 5% by mass, preferably 0.1 to 3% by mass, more preferably 0.1 to 1% by mass, and still more preferably based on the monomer mixture. 0.15 to 0.5% by mass.
- a phosphite compound, a phenol compound, a hydroxide or oxide of Mg or Zn, or the like can be mixed as a coloring inhibitor or a stabilizer.
- the polymerization temperature T (° C.) is equal to or higher than the decomposition temperature of the polymerization initiator, but is preferably set to a temperature satisfying the condition of T 10 ⁇ 25 ⁇ T ⁇ T 10 +25 with respect to T 10 of the polymerization initiator. More preferably, the temperature satisfies the condition of T 10 ⁇ 20 ⁇ T ⁇ T 10 +20, and further preferably T 10 ⁇ 15 ⁇ T ⁇ T 10 +15.
- the radical production rate from the polymerization initiator is slow, so that the reasonable productivity of the polymer [for example, the polymer yield (to be described later) within 30 hours of the polymerization time (below In some cases, it may be simply referred to as “yield.”) 70 mol% or more] to ensure a sufficient amount of polymerization initiator.
- yield. the polymerization initiator that did not contribute to the polymerization and the residue thereof remain in the polymer, and the coloration resistance and the low elution property are deteriorated.
- the end point of the polymerization reaction is appropriately selected in consideration of the balance between the decrease in the amount of unreacted monomers and the lengthening of the polymerization time, that is, the productivity of the resulting copolymer.
- the higher the polymerization temperature the shorter the polymerization time, while the lower the polymerization temperature, the longer the polymerization time.
- the polymerization time is usually 1 hour or longer, preferably 3 hours or longer, more preferably 5 hours or longer, and usually 40 hours or shorter, preferably 35 hours or shorter, more preferably 30 hours or shorter, still more preferably. Is within 25 hours.
- Polymer yield at the time of completion of polymerization (monomer mixture containing vinylidene fluoride, methylidene malonate ester and, if necessary, copolymerizable monomer)
- the ratio of the monomer is expressed in percentage.) Is usually 70 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more. If the yield is less than 70 mol%, the proportion of monomer units in the obtained vinylidene fluoride copolymer may be different from the proportion of monomer units in the vinylidene fluoride copolymer specified in the present invention. . The larger the yield, the better. However, since the polymerization time is prolonged, the upper limit is about 95 mol%, preferably 93 mol%, preferably in consideration of production restrictions. The upper limit of the yield is 90 mol%.
- the aqueous slurry containing the copolymer is heated to deactivate the polymerization initiator, and then the copolymer is filtered off, dehydrated, washed with water, and dried. A coalescent powder is obtained.
- the copolymer powder thus obtained has an average particle size [50% cumulative value (D50) in the cumulative particle size distribution when measured by the dry sieving method according to JIS (Japanese Industrial Standards, the same shall apply hereinafter) K0069.
- the average particle size represented by ] Is 30 to 250 ⁇ m, preferably 40 to 230 ⁇ m, more preferably about 50 to 200 ⁇ m, and the bulk density is 0.30 to 0.80 g / cm 3 , preferably 0.35 to 0.80 g / cm 3 , more preferably It is about 0.37 to 0.75 g / cm 3 , and the handleability is good.
- the vinylidene fluoride copolymer of the present invention is a novel vinylidene fluoride copolymer obtained by copolymerizing vinylidene fluoride, methylidene malonate ester and, if necessary, a copolymerizable monomer. is there.
- the vinylidene fluoride copolymer of the present invention usually has a melting point (Tm) measured by differential scanning calorimetry (DSC) in the range of 130 to 185 ° C. Is in the range of 163 to 177 ° C. Further, the crystallization temperature (Tc, which indicates the crystallization temperature measured in the cooling process) measured is in the range of 100 to 145 ° C., preferably in the range of 131 to 137 ° C. In particular, as the vinylidene fluoride copolymer of the present invention, a copolymer having a melting point in the range of 172 to 176 ° C.
- both the melting point and the crystallization temperature are the same as the homopolymer of vinylidene fluoride (melting point of about 174 ° C., crystallization temperature of about 136 ° C.), and the vinylidene fluoride copolymer of the present invention is a vinylidene fluoride homopolymer.
- the vinylidene fluoride copolymer of the present invention is a vinylidene fluoride homopolymer.
- the vinylidene fluoride copolymer of the present invention has a vinylidene fluoride monomer unit, a methylidene malonate monomer unit, and, if necessary, another monomer unit. Furthermore, it is characterized in that the physical properties and characteristics of the vinylidene fluoride copolymer can be designed according to the purpose of use by adjusting the types and proportions of other monomer units to be incorporated as necessary. ing.
- the vinylidene fluoride copolymer of the present invention having characteristics such as heat resistance, weather resistance, chemical resistance, stain resistance, adhesion, color reduction during molding, flexibility, etc. It is possible to provide a vinylidene fluoride copolymer according to the purpose, such as those having characteristics or those having characteristics in flexibility and color reduction during molding.
- a vinylidene fluoride copolymer having a melting point of about 130 to 168 ° C., preferably about 140 to 167 ° C., or a vinylidene fluoride copolymer having a melting point of about 178 to 185 ° C. can be obtained. It can. If desired, various vinylidene fluoride copolymers having a crystallization temperature of about 100 to 120 ° C., about 125 to 133 ° C., or about 140 to 145 ° C. can be obtained.
- the vinylidene fluoride copolymer of the present invention has a coloring resistance equivalent to that of a vinylidene fluoride homopolymer. That is, with respect to the yellow index (YI. The larger the yellow index, the stronger the yellowness) measured by a method according to ASTM D1925, the YI of the vinylidene fluoride copolymer of the present invention is less than 0 (minus).
- the difference (absolute value) between the YI of the vinylidene fluoride copolymer of the present invention and the YI of the vinylidene fluoride homopolymer is usually 30 or less, preferably 25 or less, more preferably 20 or less. .
- the vinylidene fluoride copolymer of the present invention can have the same heat decomposability as the vinylidene fluoride homopolymer. That is, regarding the thermal decomposition remaining amount at 300 ° C. in thermogravimetric analysis (TGA), the difference (absolute value) in the thermal decomposition weight change rate between the vinylidene fluoride copolymer and the vinylidene fluoride homopolymer of the present invention is Usually within 0.3%, preferably within 0.2%, more preferably within 0.1%.
- TGA thermogravimetric analysis
- the vinylidene fluoride copolymer of the present invention has excellent adhesiveness as compared with a vinylidene fluoride homopolymer.
- the peel strength with the copper foil measured by a 180 ° peel test according to JIS K6854 is 1.2 times or more, preferably 1.4 times or more, the peel strength of the vinylidene fluoride homopolymer. More preferably, it is 1.5 times or more.
- the upper limit of the peel strength varies depending on the type and amount of methylidene malonate used, but is about 4.0 times, usually considering the balance with other properties of vinylidene fluoride copolymer, 3.5 times, preferably up to about 3.0 times is useful.
- the vinylidene fluoride copolymer of the present invention can be chemically modified by reacting with various compounds using an ester group, which is a chemically reactive functional group, as the starting point of the chemical reaction. It is. As already mentioned, there have been reports of vinylidene fluoride copolymers containing ester groups, but as mentioned above, there were difficulties in heat resistance, especially coloration resistance, so the range of applicable reaction conditions Was narrow.
- the vinylidene fluoride copolymer of the present invention is useful because the heat resistance is improved and, as a result, there are few restrictions in setting reaction conditions.
- An example of chemical modification from the vinylidene fluoride copolymer of the present invention is induction into a carboxylic acid-modified vinylidene fluoride copolymer by hydrolysis of an ester group.
- the present inventors have determined that the vinylidene fluoride copolymer of the present invention has an alkali metal halide or alkali metal water such as lithium bromide, lithium iodide, lithium hydroxide, or sodium bromide.
- the carboxylic acid ester By reacting with an oxide, the carboxylic acid ester is converted to an alkali metal carboxylate, and then the resulting alkali metal carboxylate is hydrolyzed to form a methylidene malonate of the vinylidene fluoride copolymer.
- a carboxylic acid-modified vinylidene fluoride copolymer obtained by hydrolyzing 10 to 90% of the total number of ester groups in the monomer unit could be obtained.
- the ratio of the ester group of the methylidene malonate monomer unit hydrolyzed is within the range of 10 to 90%, it can be designed according to the intended use.
- a carboxylic acid-modified vinylidene fluoride copolymer characterized by improved adhesiveness can be obtained by setting the proportion of the ester group hydrolyzed to 35 to 90%, preferably about 40 to 85%. Can do.
- the vinylidene fluoride copolymer of the present invention is an organic functional group-modified vinylidene fluoride because the vinylidene fluoride is a monomer that hardly causes copolymerization with other vinyl monomers and is difficult to predict the copolymerization. It can also be positioned as an important intermediate for obtaining a copolymer.
- the functional group-modified vinylidene fluoride copolymer using the vinylidene fluoride copolymer of the present invention is obtained by a general melt molding method such as injection molding, extrusion molding or compression molding, as a film, sheet, fiber, container, or office equipment.
- a general melt molding method such as injection molding, extrusion molding or compression molding
- it can be used for the manufacture of various molded products such as parts of electronic devices, and in particular, it can be used in the fields of binders, paints, etc., because it can improve adhesion by functional group modification. Can be expected.
- Inherent viscosity refers to the logarithmic viscosity at 30 ° C. of a solution of 4 g of vinylidene fluoride copolymer dissolved in 1 liter of N, N-dimethylformamide (DMF). A sample for measurement was prepared by adding 20 ml of DMF to 80 mg of the polymer and dissolving by heating at 70 ° C. for 2 hours. The inherent viscosity was measured at 30 ° C. using an Ubbelohde viscometer manufactured by Kusano Kagaku Co., Ltd.
- Weight average molecular weight and number average molecular weight were measured using GPC (gel permeation chromatography) and calculated using polystyrene as a standard sample.
- a GPC measurement sample was prepared by dissolving 10 mg of a vinylidene fluoride copolymer in 10 ml of a LiBr-NMP solution having a concentration of 10 mM.
- GPC-900 (column; Shodex KD-806M manufactured by Showa Denko KK) ) was used at a flow rate of 1 ml / min and a measurement temperature of 40 ° C.
- the DSC measurement sample was preheated at 210 ° C for 30 seconds using a press molding machine (AYSR-5, manufactured by Shindo Metal Industry Co., Ltd.), and then held at a press pressure of 0.5 MPa for 1 minute to produce a press sheet. And about 10 mg was cut out from there and produced.
- DSC measurement was performed using a DSC30 manufactured by METTTLER in a nitrogen atmosphere at a rate of 10 ° C./min in the range of 30 to 220 ° C., and the melting point ( Tm) was determined, and the crystallization temperature (Tc) was determined from the exothermic peak temperature in the cooling process.
- Thermal decomposition weight loss The thermal decomposition weight loss of the vinylidene fluoride copolymer was measured by thermogravimetric analysis (TGA).
- the TGA measurement sample was prepared by cutting out approximately 20 mg of the sample from the press sheet prepared as the DSC measurement sample, and using a thermogravimetric analyzer (TGA / SDTA851 manufactured by METTTLER TOLEDO) in a nitrogen atmosphere. The temperature was raised at a rate of ° C./min, and the thermal decomposition loss of the sample was measured.
- NMR Nuclear Magnetic Resonance
- IR spectrum A sample for IR spectrum measurement of a vinylidene fluoride copolymer was prepared as a press film having a thickness of about 0.05 mm by a press molding machine (AYSR-5, manufactured by Shinto Metal Industry Co., Ltd.). . The IR spectrum was measured using FT-730 manufactured by HORIBA (Horiba, Ltd.).
- Yellow index (YI) A sample for measuring YI of vinylidene fluoride copolymer is pre-heated at 240 ° C. for 6 minutes using a press molding machine (AYSR-5, manufactured by Shinfuji Metal Industry Co., Ltd.) and then held at a press pressure of 10 MPa for 2 minutes. Thus, a test piece of 11 ⁇ 6.4 ⁇ 0.6 cm was produced.
- YI was measured by a method according to ASTM D1925 using color meter ZE6000 manufactured by Nippon Denshoku Industries Co., Ltd. The larger the YI value, the stronger the yellowness.
- Electrode composition 96 parts of artificial graphite (MCMB25-28 manufactured by Osaka Gas Chemical Co., Ltd.) and 4 parts of vinylidene fluoride copolymer were dispersed in a solvent NMP to obtain a solid.
- An electrode slurry having a partial concentration of 63% by mass was prepared, coated on a Cu foil having a thickness of 10 ⁇ m with a bar coater, and dried at 110 ° C. for 30 minutes to prepare a single-side coated electrode having a single-sided weight of 150 g / m 2 .
- the single-side coated electrode obtained above was cut into a length of 50 mm and a width of 20 mm, and plane-pressed at room temperature and a press pressure of 0.8 t / cm 2 to obtain a test piece. Gum tape is applied to the coated electrode surface, and Cu foil is used as a “flexible adherend, using a tensile tester (STA-1150 UNIVERSAL TESTING MACHINE manufactured by ORIENTEC) according to JIS K6854, at a head speed of 200 mm / min. A peel test was conducted to measure the peel strength.
- the polymer slurry is heat treated at 95 ° C. for 30 minutes to deactivate the polymerization initiator, and then the polymer is filtered, dehydrated and washed, and further dried at 80 ° C. for 20 hours. A polymer powder was obtained. The yield was 86%, and the inherent viscosity of the obtained polymer was 1.29 dl / g.
- Example 2 to 4 Comparative Examples 1 to 3 were performed in the same manner as in Example 1 except that vinylidene fluoride (VDF), comonomer ratio, and comonomer type were changed as shown in Table 1. .
- the comparative example 1 is a homopolymer of vinylidene fluoride.
- Example 1 the copolymer of methylidene malonate ester was obtained in Example 1 with COOCH 2 R in the 1 H-NMR spectrum of the obtained polymer.
- the ratio (molar ratio) between the vinylidene fluoride unit and the methylidene malonate unit contained in the vinylidene fluoride copolymer was calculated by the area ratio in the 1 H-NMR spectrum.
- the ratio of chlorotrifluoroethylene units was calculated from the chlorine concentration measured by the oxygen flask combustion method.
- Table 2 summarizes various physical properties and characteristics of the polymers obtained in Examples 1 to 4 and Comparative Examples 1 to 3.
- the vinylidene fluoride copolymers of the present invention of Examples 1 to 3 have almost the same melting point and crystallization temperature as compared with the vinylidene fluoride homopolymer of Comparative Example 1 by only 1 to 2 ° C. Maintains heat resistance and moldability. Further, the vinylidene fluoride copolymer of the present invention having another monomer unit of Example 4 has practically heat resistance with a melting point of 165 ° C. and a relatively low crystallization temperature of 131 ° C. Thus, a copolymer that can be used for the production of a molded product having high crystallinity and high strength and for applications that require flexibility was obtained.
- the vinylidene fluoride copolymers of the present invention of Examples 1 to 4 are different from the vinylidene fluoride homopolymer of Comparative Example 1 in terms of YI indicating coloration resistance by 12.8 to 19.9. Since it is small and has a negative value, the color resistance is also at a sufficient level.
- the vinylidene fluoride copolymer of Example 1 is almost the same as the homopolymer of vinylidene fluoride of Comparative Example 1 by heating above 300 ° C. Less weight loss and excellent heat resistance equivalent to vinylidene fluoride homopolymer. Furthermore, when the peel strength between the coated electrode and the copper foil using the vinylidene fluoride copolymer of Example 1 as a binder was measured by a 180 ° peel test in accordance with JIS K6854, it was 4.14 gf / mm.
- Example 4 is a vinylidene fluoride copolymer of the present invention having chlorotrifluoroethylene as another monomer. It is known that the crystallinity can be lowered by copolymerizing chlorotrifluoroethylene with vinylidene fluoride, and it is applied to applications where flexibility is more important than high heat resistance. Applications requiring such flexibility include tubes (for example, JP-A-6-73135; corresponding to US Pat. No. 5,292,816) and polymer gel electrolytes (for example, JP-A-11-66949). ) Can be exemplified.
- the vinylidene fluoride copolymer obtained by copolymerizing the maleate ester of Comparative Examples 2 and 3 is almost equivalent to the homopolymer in Tm and Tc, but the YI value shows a large plus. Colorability was inferior and practicality was poor.
- the vinylidene fluoride copolymer of Comparative Example 2 rapidly loses weight when it exceeds 300 ° C. from the TGA pyrolysis curve of FIG.
- Example 5 A 500 ml three-necked flask equipped with a magnetic stir bar and a Dimroth condenser was charged with 125 ml of N, N-dimethylformamide and 1.17 g of lithium bromide to form a solution. To this solution, 5.05 g of the vinylidene fluoride copolymer of the present invention obtained in Example 2 was added, and the mixture was heated and stirred at 100 ° C. for 9 hours. After cooling to room temperature, the reaction solution was reprecipitated using dilute hydrochloric acid. The obtained solid was separated by filtration, dehydrated and washed with water, and further dried at 80 ° C. for 20 hours.
- the physical properties of the obtained modified vinylidene fluoride copolymer are as shown in Table 3. It was found that the modified vinylidene fluoride copolymer had a melting point and a crystallization temperature equivalent to those of the vinylidene fluoride copolymer before modification in Example 2. For this reason, the modified vinylidene fluoride copolymer can be subjected to various chemical modifications while maintaining the same excellent heat resistance as the homopolymer of vinylidene fluoride and the vinylidene fluoride copolymer before modification. Is inferred.
- the vinylidene fluoride copolymer having a vinylidene fluoride monomer unit and a methylidene malonate monomer unit of the present invention is excellent in heat resistance, weather resistance, chemical resistance, stain resistance, and good adhesion. Since coloring during molding is reduced, it can be expected to be widely used in the fields of various molded products, binders, paints and the like.
- ester group possessed by the vinylidene fluoride copolymer of the present invention is a chemically reactive functional group, various chemical modifications are possible using the ester group as a starting point for a chemical reaction. It can be expected to be applied to solving a wider range of fields and issues.
- the vinylidene fluoride copolymer of the present invention can be produced by a suspension polymerization method employing the same conditions as before without requiring special production facilities, etc. It can be expected to be applied to solving a wider range of fields and issues.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
式(1)で示されるフッ化ビニリデン単量体単位99.9~90モル%、式(2)で示されるメチリデンマロン酸エステル単量体単位0.1~10モル%、及び前記単量体単位以外の単量体単位0~10モル%とを有する、重量平均分子量が200,000以上であるフッ化ビニリデン共重合体の製造方法が提供される。
本発明の新規なフッ化ビニリデン共重合体は、先の式(1)で示されるフッ化ビニリデン単量体単位99.9~90モル%、式(2)で示されるメチリデンマロン酸エステル単量体単位0.1~10モル%、及び前記単量体単位以外の単量体単位0~10モル%とを有する、重量平均分子量Mwが200,000以上であるフッ化ビニリデン共重合体である。本発明のフッ化ビニリデン共重合体は、好ましくはフッ化ビニリデン単量体単位99.9~92モル%及びメチリデンマロン酸エステル単量体単位0.1~8モル%とを有し、より好ましくはフッ化ビニリデン単量体単位99.8~94モル%及びメチリデンマロン酸エステル単量体単位0.2~6モル%、更に好ましくはフッ化ビニリデン単量体単位99.8~96モル%及びメチリデンマロン酸エステル単量体単位0.2~4モル%、特に好ましくはフッ化ビニリデン単量体単位99.8~99モル%及びメチリデンマロン酸エステル単量体単位0.2~1モル%とを有するフッ化ビニリデン共重合体である。フッ化ビニリデン単量体単位が99.9モル%を超えると、フッ化ビニリデンの単独重合体に近づくことから、金属等との接着性が良好でなく、他方、フッ化ビニリデン単量体単位が90モル%未満であると、耐熱性や耐薬品性が不十分であり、成形加工時に着色が生ずることがある。
式(2)のメチリデンマロン酸エステル単量体単位を形成する単量体は、式(3)で表されるメチリデンマロン酸エステルである。式(3)において、R1及びR2は、それぞれ独立に、H、または炭素数1~5の脂肪族炭化水素基であり、メチリデンマロン酸のジエステルとモノエステルとを含む。R1及びR2が同時にHである場合は、式(3)で表されるメチリデンマロン酸エステルの範疇に含まれない。R1及びR2としては、安定性よく、短時間で重合体を得ることができることから、メチル基、エチル基及びプロピル基が好ましい。これに対して、R1またはR2が炭素数6以上の脂肪族炭化水素基であると、エステル部分が嵩高となる結果、メチリデンマロン酸エステルへのフッ化ビニリデンラジカル等の付加が阻害される結果、重合時間が長期化する、または、メチリデンマロン酸エステルへの付加が全く起こらず、フッ化ビニリデンのみで重合が進行し、フッ化ビニリデン単独重合体が得られてしまう等のため、実用性がない。なお、本発明の効果は、メチリデンマロン酸エステルのみならず、エチリデンマロン酸エステルやプロピリデンマロン酸エステルなどの他のアルキリデンマロン酸エステルでも同様に得ることができる。
a.中間体の合成
ジムロート冷却管と磁気撹拌子を備えた500ml三口フラスコに、マロン酸ジメチル66.2g(0.501mol)、アントラセン89.7g(0.503mol)、パラホルムアルデヒド30.0g(ホルムアルデヒドとして1.00mol)、酢酸銅(II)一水和物5.00g(25mmol)、酢酸112ml、及び、キシレン112mlを入れ、24時間加熱還流した。反応終了後に得られる粗生成物をエタノールにより再結晶することにより、中間体の化合物を無色針状結晶として得た。収量107g、収率67%であった。
ジムロート冷却管と磁気撹拌子を備えた500ml三口フラスコに、先の中間体化合物40.0g(0.124mol)、無水マレイン酸14.6g(0.149mol)、及び、流動パラフィン200mlを入れ、225℃で窒素雰囲気下、1.5時間加熱撹拌した。反応終了後、減圧蒸留(66-68℃/10hPa)により、メチリデンマロン酸ジメチルを無色油状物として得た。収量12.4g、収率69%であった。
本発明のフッ化ビニリデン共重合体は、少なくとも、フッ化ビニリデン99.9~90モル%、式(3)で示されるメチリデンマロン酸エステル0.1~10モル%、及び、共重合可能な単量体0~10モル%とを含有する単量体混合物、並びに重合開始剤を、分散安定剤を含む水性媒体に分散させ、重合反応を行うことにより製造することができる。
単量体混合物は、少なくとも、フッ化ビニリデン99.9~90モル%、式(3)で示されるメチリデンマロン酸エステル0.1~10モル%、及び、共重合可能な単量体0~10モル%とを含有する単量体混合物である。
重合開始剤としては、10時間半減期温度T10が30℃(ほぼフッ化ビニリデンの臨界温度に相当する。)~90℃のものが好ましく用いられ、ジイソプロピルパーオキシジカーボネート(T10=40.5℃)、ジノルマルプロピルパーオキシジカーボネート(T10=40.3℃)、パーブチルパーオキシピバレート(T10=54.6℃)が挙げられ、所望の重合温度に応じて適宜選択し、使用される。重合開始剤の使用量は、できるだけ少ないことが熱安定性の良いフッ化ビニリデン共重合体を得るために好ましいが、少な過ぎると重合時間が極端に長くなるので、単量体混合物の量に対し、0.01~2質量%の範囲が好ましく、より好ましくは0.05~1.5質量%、更に好ましくは0.1~1.2質量%の範囲である。重合開始剤が、2質量%を超えると、重合反応で有効に使い切ることが困難になり、結果的に得られる重合体の高温耐着色性や溶出性が悪化しがちである。
分散安定剤としては、重合反応として乳化重合を行うときは、汎用のフッ素系乳化剤を使用することができる。また、重合反応として懸濁重合を行うときは、通常の懸濁重合に用いられる懸濁剤を使用することができ、部分鹸化ポリ酢酸ビニル、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース等の水溶性セルロースエーテル、アクリル酸系重合体、ゼラチン等の水溶性ポリマーを例示できる。懸濁剤の使用量は、単量体混合物の量に対し、通常0.01~2質量%、好ましくは0.01~1質量%、より好ましくは0.05~0.5質量%の割合で用いられる。
水性媒体としては、通常のイオン交換水、蒸留水または超純水などを用いることができる。水性媒体の使用量は、水性媒体/単量体混合物の比(質量比)が、通常1/1~10/1であり、好ましくは1.5/1~8/1、より好ましくは2/1~6/1、特に好ましくは2.5/1~5/1の範囲である。水性媒体/単量体混合物の比が、1/1未満では、撹拌や除熱や粒径制御が困難となる。また、前記比が、10/1を超えると、製造効率が低下するなどの問題がある。
本発明のフッ化ビニリデン共重合体を懸濁重合によって製造するときは、得られる共重合体の分子量を調節する目的で、連鎖移動剤を使用することが好ましい。連鎖移動剤としては、アセトン、酢酸イソプロピル、酢酸エチル、炭酸ジエチル、炭酸ジメチル、焦性炭酸エチル、プロピオン酸、トリフロロ酢酸、トリフロロエチルアルコール、ホルムアルデヒドジメチルアセタール、1,3-ブタジエンエポキサイド、1,4-ジオキサン、β-ブチルラクトン、エチレンカーボネート、ビニレンカーボネート等が挙げられるが、効果的に分子量またはインヘレント粘度を低下させ、かつフッ化ビニリデン共重合体の熱安定性を阻害しないこと、入手の容易さ、取り扱いの容易さを考慮すると、アセトン、酢酸エチル、炭酸ジエチルがより好ましく、特に酢酸エチル、炭酸ジエチルが好ましい。連鎖移動剤の使用量は、単量体混合物に対して、0.05~5質量%であり、好ましくは0.1~3質量%、より好ましくは0.1~1質量%、更に好ましくは0.15~0.5質量%である。
本発明のフッ化ビニリデン共重合体を懸濁重合方法によって製造するには、フッ化ビニリデン(臨界温度Tc=30.1℃、臨界圧力Pcr=4.38MPa)99.9~90モル%、式(3)のメチリデンマロン酸エステル0.1~10モル%、及び、共重合可能な単量体0~10モル%との混合物(以下、「モノマー混合物」という。)100質量部を、水性媒体100~1000質量部、好ましくは150~800質量部、より好ましくは200~600質量部、特に好ましくは250~500質量部中に分散させて、重合温度まで昇温して懸濁重合を開始させる。
本発明のフッ化ビニリデン共重合体は、通常、示差走査熱量測定(DSC)により測定される融点(Tm)が、130~185℃の範囲にあり、好ましくは163~177℃の範囲にある。また、測定される結晶化温度(Tc。冷却過程で測定される結晶化温度を指す。)が、100~145℃の範囲にあり、好ましくは131~137℃の範囲にある。特に、本発明のフッ化ビニリデン共重合体としては、融点が172~176℃の範囲内であって、結晶化温度が、131~137℃の範囲内のものを得ることができる。この場合、融点、結晶化温度ともにフッ化ビニリデン単独重合体と同等(融点174℃程度、結晶化温度136℃程度)であり、本発明のフッ化ビニリデン共重合体は、フッ化ビニリデン単独重合体と同等の成形加工条件で成形することができる。
本発明のフッ化ビニリデン共重合体は、化学的に反応活性な官能基であるエステル基を化学反応の基点として、様々な化合物との反応による化学変性が可能である。既に述べたように、これまでもエステル基を含有するフッ化ビニリデン共重合体の報告はあるが、上述のように、耐熱性、特に耐着色性に難があったため、適用可能な反応条件範囲が狭かった。本発明のフッ化ビニリデン共重合体は、耐熱性が改良されている結果、反応条件の設定における制約が少ないので、有用である。
インヘレント粘度は、フッ化ビニリデン共重合体4gを1リットルのN,N-ジメチルホルムアミド(DMF)に溶解させた溶液の30℃における対数粘度をいう。測定用サンプルは、重合体80mgにDMF20mlを加え、70℃で2時間加熱溶解して、調製した。インヘレント粘度の測定は、株式会社草野科学製ウベローデ型粘度計を用いて30℃で行った。
重量平均分子量及び数平均分子量は、GPC(ゲルパーミエイションクロマトグラフィー)を利用して測定を行い、ポリスチレンを標準サンプルとして算出した。
フッ化ビニリデン共重合体の融点(Tm)及び結晶化温度(Tc)は、示差走査熱量測定(DSC)により測定した。
フッ化ビニリデン共重合体の熱分解減量を熱重量分析(TGA)によって測定した。
フッ化ビニリデン共重合体のNMRスペクトルの測定は、測定溶媒として市販の重DMFをそのまま用い、Bruker社製AVANCE AC 400FT NMRスペクトルメータを用いて行った。
フッ化ビニリデン共重合体のIRスペクトル測定用サンプルは、プレス成型機(株式会社神藤金属工業製、AYSR-5)により厚さ約0.05mmプレスフィルムとして作製した。IRスペクトルの測定は、HORIBA(株式会社堀場製作所)製FT-730を用いて行った。
フッ化ビニリデン共重合体のYIの測定用サンプルは、プレス成型機(株式会社神藤金属工業製AYSR-5)を使用し、240℃で6分間予備加熱した後、プレス圧10MPaで2分間保持することにより11×6.4×0.6cmの試験片として作製した。
電極組成として、人造黒鉛(大阪ガスケミカル株式会社製MCMB25-28)96部、フッ化ビニリデン共重合体4部の組成を与える各試料を溶媒NMP中に分散させ、固形分濃度63質量%の電極スラリーを調製し、厚み10μmのCu箔上にバーコーターで塗布し、110℃で30分間乾燥し、片面目付け量が150g/m2の片面塗工電極を作製した。
[実施例1](フッ化ビニリデン/メチリデンマロン酸ジメチル=99/1(質量比))
内容量2リットルのオートクレーブに、イオン交換水1024g、メチルセルロース0.6g、酢酸エチル1.2g、50wt%ジイソプロピルパーオキシジカーボネイト-フロン225cb溶液8.6g、フッ化ビニリデン(VDF)396g、メチリデンマロン酸ジメチル4.0gを仕込み、29℃で、圧力が1.5MPaに下がるまで、22時間の懸濁重合を行った。重合完了後、重合体スラリーを95℃で30分間熱処理して、重合開始剤を失活させた後、重合体をろ別し、脱水と水洗を行い、更に80℃で20時間乾燥することにより、重合体粉末を得た。収率は86%で、得られた重合体のインヘレント粘度は1.29dl/gであった。
実施例2~4、比較例1~3は、フッ化ビニリデン(VDF)とコモノマー比、およびコモノマーの種類を、表1に記載のとおり変更した以外は、実施例1と同様の方法で行った。なお、比較例1は、フッ化ビニリデンの単独重合体である。
実施例1~4及び比較例1~3で得られた重合体の各種物性及び特性を表2にまとめる。
[実施例5]
磁気攪拌子とジムロート冷却管を備えた500ml三口フラスコに、N,N-ジメチルホルムアミド125ml、及び臭化リチウム1.17gを入れ、溶液とした。この溶液に、実施例2で得られた本発明のフッ化ビニリデン共重合体5.05gを入れ、100℃で9時間加熱攪拌した。室温まで放冷した後、反応溶液を、希塩酸を用いて再沈操作を行った。得られた固体をろ別して分取し、脱水と水洗を行い、更に80℃で20時間乾燥した。得られた固体の1H-NMRスペクトルを測定したところ、COOCH3に帰属するシグナル(3.7ppm付近)の積分値の変化から、共重合体中のエステル基の数の総数の約41%が加水分解されていることを確認した(図5及び図6を参照)。
Claims (10)
- 融点が、163~177℃の範囲である請求項1記載のフッ化ビニリデン共重合体。
- 剥離強度が、メチリデンマロン酸エステル単量体単位を有しないフッ化ビニリデン単独重合体の1.2倍以上である請求項1記載のフッ化ビニリデン共重合体。
- R1及びR2が、メチル基である請求項1記載のフッ化ビニリデン共重合体。
- R1及びR2が、エチル基である請求項1記載のフッ化ビニリデン共重合体。
- 請求項1記載のフッ化ビニリデン共重合体において、前記式(2)で示されるメチリデンマロン酸エステル単量体単位が有するエステル基の総数の10~90%が加水分解されて成る、変性フッ化ビニリデン共重合体。
- フッ化ビニリデン99.9~90モル%、式(3)で示されるメチリデンマロン酸エステル0.1~10モル%、及び、他の共重合可能な単量体0~10モル%とを含有する単量体混合物、並びに重合開始剤を、分散安定剤を含む水性媒体に分散させ、重合開始剤の分解温度以上の重合温度に昇温して重合反応を行う、
式(1)で示されるフッ化ビニリデン単量体単位99.9~90モル%、式(2)で示されるメチリデンマロン酸エステル単量体単位0.1~10モル%、及び前記単量体単位以外の単量体単位0~10モル%とを有する、重量平均分子量が200,000以上であるフッ化ビニリデン共重合体の製造方法。
- 前記重合温度が、以下の式(4)を満足する温度である請求項7記載のフッ化ビニリデン共重合体の製造方法。
T10-25≦T≦T10+25 ・・・・・・(4)
(ただし、Tは、重合温度(℃)を意味し、T10は、重合開始剤の10時間半減期温度(℃)を意味する。) - 重合反応終了時の重合体収率が70モル%以上である請求項7記載のフッ化ビニリデン共重合体の製造方法。
- 請求項7記載のフッ化ビニリデン共重合体の製造方法において、更に、アルカリ金属ハロゲン化物またはアルカリ金属水酸化物を用いて、式(2)で示されるメチリデンマロン酸エステル単量体単位が有するエステル基の総数の10~90%を加水分解する、変性フッ化ビニリデン共重合体の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011535363A JP5639069B2 (ja) | 2009-10-09 | 2010-09-30 | 新規なフッ化ビニリデン共重合体及びその製造方法 |
KR1020127011862A KR101385921B1 (ko) | 2009-10-09 | 2010-09-30 | 신규의 불화 비닐리덴 공중합체 및 그 제조 방법 |
CN201080045460.6A CN102574958B (zh) | 2009-10-09 | 2010-09-30 | 新的1,1-二氟乙烯共聚物及其制造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009235658 | 2009-10-09 | ||
JP2009-235658 | 2009-10-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011043246A1 true WO2011043246A1 (ja) | 2011-04-14 |
Family
ID=43856704
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/067154 WO2011043246A1 (ja) | 2009-10-09 | 2010-09-30 | 新規なフッ化ビニリデン共重合体及びその製造方法 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP5639069B2 (ja) |
KR (1) | KR101385921B1 (ja) |
CN (1) | CN102574958B (ja) |
WO (1) | WO2011043246A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015103464A (ja) * | 2013-11-27 | 2015-06-04 | 株式会社クレハ | フッ化ビニリデン系重合体水系組成物およびその用途 |
JP2016535814A (ja) * | 2013-10-30 | 2016-11-17 | スリーエム イノベイティブ プロパティズ カンパニー | 非フッ素化ポリヒドロキシ乳化剤を使用した重合によって得ることができる過酸化物硬化性フルオロポリマー |
JP2017527668A (ja) * | 2014-09-08 | 2017-09-21 | シラス・インコーポレイテッド | 1つ以上の1,1−二置換アルケン化合物を含むポリマー及びそのポリマー組成物 |
JP2019509365A (ja) * | 2016-01-25 | 2019-04-04 | アルケマ フランス | フィルムに接着性を付与するためのフッ化ビニリデンコポリマーの使用 |
US10308802B2 (en) | 2014-09-08 | 2019-06-04 | Sirrus, Inc. | Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104448094A (zh) * | 2014-12-06 | 2015-03-25 | 常熟丽源膜科技有限公司 | 用于生产热稳定性聚偏氟乙烯的工艺 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06172452A (ja) * | 1992-12-02 | 1994-06-21 | Kureha Chem Ind Co Ltd | フッ化ビニリデン系共重合体 |
JPH11193312A (ja) * | 1997-10-15 | 1999-07-21 | E I Du Pont De Nemours & Co | 無水マレイン酸またはマレイン酸とフッ素化されたオレフィンとの共重合体 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0016876D0 (en) * | 2000-07-11 | 2000-08-30 | Astrazeneca Ab | Novel formulation |
JP5219374B2 (ja) * | 2005-07-20 | 2013-06-26 | 株式会社Adeka | 含フッ素共重合体、アルカリ現像性樹脂組成物及びアルカリ現像性感光性樹脂組成物 |
JP5346192B2 (ja) * | 2007-10-05 | 2013-11-20 | ローム アンド ハース カンパニー | 改善されたポリマー組成物 |
-
2010
- 2010-09-30 CN CN201080045460.6A patent/CN102574958B/zh not_active Expired - Fee Related
- 2010-09-30 KR KR1020127011862A patent/KR101385921B1/ko not_active IP Right Cessation
- 2010-09-30 WO PCT/JP2010/067154 patent/WO2011043246A1/ja active Application Filing
- 2010-09-30 JP JP2011535363A patent/JP5639069B2/ja not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06172452A (ja) * | 1992-12-02 | 1994-06-21 | Kureha Chem Ind Co Ltd | フッ化ビニリデン系共重合体 |
JPH11193312A (ja) * | 1997-10-15 | 1999-07-21 | E I Du Pont De Nemours & Co | 無水マレイン酸またはマレイン酸とフッ素化されたオレフィンとの共重合体 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016535814A (ja) * | 2013-10-30 | 2016-11-17 | スリーエム イノベイティブ プロパティズ カンパニー | 非フッ素化ポリヒドロキシ乳化剤を使用した重合によって得ることができる過酸化物硬化性フルオロポリマー |
JP2015103464A (ja) * | 2013-11-27 | 2015-06-04 | 株式会社クレハ | フッ化ビニリデン系重合体水系組成物およびその用途 |
WO2015079936A1 (ja) * | 2013-11-27 | 2015-06-04 | 株式会社クレハ | フッ化ビニリデン系重合体水系組成物およびその用途 |
JP2017527668A (ja) * | 2014-09-08 | 2017-09-21 | シラス・インコーポレイテッド | 1つ以上の1,1−二置換アルケン化合物を含むポリマー及びそのポリマー組成物 |
EP3191533A4 (en) * | 2014-09-08 | 2018-03-07 | Sirrus, Inc. | Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof |
US10308802B2 (en) | 2014-09-08 | 2019-06-04 | Sirrus, Inc. | Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof |
JP2020117721A (ja) * | 2014-09-08 | 2020-08-06 | シラス・インコーポレイテッド | 1つ以上の1,1−二置換アルケン化合物を含むポリマー及びそのポリマー組成物 |
US11021617B2 (en) | 2014-09-08 | 2021-06-01 | Sirrus, Inc. | Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof |
JP2019509365A (ja) * | 2016-01-25 | 2019-04-04 | アルケマ フランス | フィルムに接着性を付与するためのフッ化ビニリデンコポリマーの使用 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2011043246A1 (ja) | 2013-03-04 |
CN102574958B (zh) | 2014-07-16 |
KR101385921B1 (ko) | 2014-04-15 |
CN102574958A (zh) | 2012-07-11 |
KR20120066064A (ko) | 2012-06-21 |
JP5639069B2 (ja) | 2014-12-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5639069B2 (ja) | 新規なフッ化ビニリデン共重合体及びその製造方法 | |
EP1432744B2 (en) | Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers | |
US9394394B2 (en) | Synthesis of chlorotrifluoroethylene-based block copolymers by iodine transfer polymerization | |
JP2012067324A (ja) | 低結晶度の弗化ビニリデンヘキサフルオルプロピレン共重合体 | |
JP6371295B2 (ja) | 溶媒を含むペルオキシド硬化性フルオロポリマー組成物及びその使用方法 | |
WO2012114441A1 (ja) | 懸濁重合用分散剤、塩化ビニル系樹脂及びその製造方法 | |
WO2010113819A1 (ja) | 新規なポリビニルアルコール系重合体およびその製造方法 | |
KR102443892B1 (ko) | 비닐리덴 플루오라이드 중합체 | |
JP2014031487A (ja) | 変性ポリ酢酸ビニル | |
JP5236250B2 (ja) | 重合用分散剤、これを用いた塩化ビニル系樹脂の製造方法、塩化ビニル系樹脂並びに成形加工品 | |
JP4683735B2 (ja) | フッ化ビニリデン重合体及びその製造方法 | |
JP3379883B2 (ja) | フッ化ビニリデン系樹脂の製造方法 | |
WO2015005153A1 (ja) | ビニルアセタール系重合体 | |
JP5320227B2 (ja) | 耐酸着色性の優れたフッ化ビニリデン重合体の製造方法 | |
KR20210034418A (ko) | 염화비닐계 중합체의 제조방법 | |
JP2011246512A (ja) | 塩化ビニル系重合体 | |
TW555769B (en) | Vinylidene fluoride polymers, process for manufacturing them and use thereof | |
JPH10101715A (ja) | 塩化ビニル系重合体の製造法 | |
JP2015187215A (ja) | 変性ポリ酢酸ビニル | |
TW202110919A (zh) | 乙烯醇系嵌段共聚物及其製造方法 | |
CN115368493A (zh) | 一种耐开裂乙烯-三氟氯乙烯共聚物、组合物及制备方法 | |
JP2000302805A (ja) | 塩化ビニル系樹脂の製造法 | |
JPS61113607A (ja) | フルオロオレフイン共重合体及びその製造法 | |
JP2000143710A (ja) | 塩化ビニル系樹脂の製造方法 | |
JPH0757786B2 (ja) | 含フツ素共重合体の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080045460.6 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10821917 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011535363 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20127011862 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10821917 Country of ref document: EP Kind code of ref document: A1 |