JPS6354409A - Fluorinated copolymer - Google Patents
Fluorinated copolymerInfo
- Publication number
- JPS6354409A JPS6354409A JP16824887A JP16824887A JPS6354409A JP S6354409 A JPS6354409 A JP S6354409A JP 16824887 A JP16824887 A JP 16824887A JP 16824887 A JP16824887 A JP 16824887A JP S6354409 A JPS6354409 A JP S6354409A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- copolymer
- mol
- fluorine
- structural units
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title abstract description 45
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 26
- 239000011737 fluorine Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 21
- 239000003973 paint Substances 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 abstract description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 abstract description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 10
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 8
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 for example Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、塗料材料に適する官能基含有含フツ素共重合
体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a functional group-containing fluorine-containing copolymer suitable for coating materials.
従来、耐候性を有する常温硬化性塗料用材料として、フ
ルオロオレフィン、シクロヘキシルビニルエーテルおよ
びその他種々の単量体を共重合した共重合体が提案され
ている（特開昭５５−２５４１４、同５７−３４１０７
および同５７−３４１０８号公報）、シかし、この共重
合体は、塗料の透光性を向上させるためによく使用され
るメチルメタクリレート系重合体と相溶性が良（ないと
いう問題を有している。Conventionally, copolymers made by copolymerizing fluoroolefins, cyclohexyl vinyl ether, and various other monomers have been proposed as weather-resistant room-temperature-curing paint materials (JP-A-55-25414, JP-A-57-34107).
However, this copolymer does not have good compatibility with methyl methacrylate polymers, which are often used to improve the transparency of paints. ing.
本発明者らは、メチルメタクリレート系重合体と相溶性
の良い含フツ素共重合体を探した結果、特定のＪＡ量体
を含有する含フツ素共重合体がこの性質に優れているこ
とを見出し、本発明に達したものである。The present inventors searched for a fluorine-containing copolymer that has good compatibility with methyl methacrylate polymers, and found that a fluorine-containing copolymer containing a specific JA polymer has excellent properties. Heading: This is what led to the present invention.
本発明の目的は、塗料材料等として優れている含フツ素
共重合体を提供することである。An object of the present invention is to provide a fluorine-containing copolymer that is excellent as a coating material and the like.
本発明に係わる含フツ素共重合体は、式：％式％（）
で表わされる構造華位５０〜９９モル％および式ニ
ーＣＣ００Ｈ、ｍは０または１〜１０の整数、ｎは１〜
４の整数を示す。）
で表わされる構造単位１〜５０モル％および式：％式％
（）
（式中、Ｙは塩素、フッ素またはトリフルオロメチル基
を示す、）
で表わされる構造単位３０モル％以下（ただし、構造華
位（ａ）、（ｂ）および（ｃ）の合計は１００モル％で
ある。）から木質的に構成される、分子量１０，０００
〜５００．０００の含フツ素ランダム共重合体である。The fluorine-containing copolymer according to the present invention has a structure represented by the formula % formula % () with a structure of 50 to 99 mol % and a formula of CC00H, m is 0 or an integer of 1 to 10, and n is 1 to
Indicates an integer of 4. ) Structural units represented by 1 to 50 mol% and formula:% formula%
() (wherein, Y represents chlorine, fluorine or trifluoromethyl group) 30 mol% or less of structural units (However, the total of structural positions (a), (b) and (c) is 100 mol% or less mol%), with a molecular weight of 10,000.
~500,000 fluorine-containing random copolymer.
本発明の含フツ素共重合体は、１．１−ジフルオロエチ
レン、式：
％式％
（式中、Ｘ、ｍおよびｎは前記と同じ、）で表わされる
官能基を有する単量体および弐：ＣＦ、、ＣＦＹ
（式中、Ｙは前記と同じ、）
で表わされるフルオロオレフィンを共重合させて得るこ
とができ、通常分子量は、ゲルパーミェーションクロマ
トグラフィー（ＧＰＣ）による測定でｔｏ、ｏｏｏ〜５
００，０００ 、ガラス転移点は、−４０〜７０℃であ
る。また、前記単量体の他、本発明の含フツ素共重合体
の物性を損なわない範囲で他の単量体を共重合してもよ
い。The fluorine-containing copolymer of the present invention comprises 1,1-difluoroethylene, a monomer having a functional group represented by the formula: % formula % (wherein X, m and n are the same as above) and It can be obtained by copolymerizing fluoroolefins represented by: CF,, CFY (in the formula, Y is the same as above), and the molecular weight is usually determined by gel permeation chromatography (GPC) to, ooo~5
00,000, the glass transition point is -40 to 70°C. In addition to the above-mentioned monomers, other monomers may be copolymerized as long as the physical properties of the fluorine-containing copolymer of the present invention are not impaired.
本発明の含フツ素共重合体は、乳化、懸濁または溶液重
合で製造することができる。重合温度は、いずれの方法
でも通常Ｏ〜１５０℃、好ましくは５〜９５℃、重合圧
力も、いずれの方法でも通常５０ｋｇ／ｃｍ”Ｇ以下で
ある。The fluorine-containing copolymer of the present invention can be produced by emulsion, suspension or solution polymerization. In either method, the polymerization temperature is usually 0 to 150°C, preferably 5 to 95°C, and the polymerization pressure is usually 50 kg/cm''G or less in any method.
重合媒体は、懸濁重合では、例えば水、１．１．２−ト
リクロロ−１，２，２−トリフルオロエタンまたは１゜
２−ジクロロ−１，１，２，２−テトラフルオロエタン
あるいはこれらの混合物等、溶液重合では、例えばメチ
ルエヂルケトン、酢酸エチル、酢酸ブチル等である。In suspension polymerization, the polymerization medium is, for example, water, 1.1.2-trichloro-1,2,2-trifluoroethane or 1.2-dichloro-1,1,2,2-tetrafluoroethane or these. In the case of solution polymerization of mixtures, for example, methyl ethyl ketone, ethyl acetate, butyl acetate, etc. are used.
重合開始剤は、乳化重合では、酸化剤、還元剤および遷
移金属塩類からなるレドックス開始剤等、懸濁および溶
液重合では、アゾ系化合物や有機過酸化物等である。酸
化剤の例としては、過硫酸アンモニウム、過硫酸カリ等
の過硫酸塩、還元剤の例としては、亜硫酸ナトリウム等
の亜硫酸塩、遷移金属塩類の例としては、硫酸鉄（Ｉｒ
）等、アゾ系化合物の例としては、アゾビスイソブチロ
ニトリル等、有機過酸化物の例としては、イソ−ブチリ
ルパーオキシド、オククノイルパーオキシド、ジ−イソ
−プロピルパーオキシ−ジ−カーボネート等が挙げられ
る。The polymerization initiator is a redox initiator consisting of an oxidizing agent, a reducing agent, and a transition metal salt in emulsion polymerization, and an azo compound or an organic peroxide in suspension or solution polymerization. Examples of oxidizing agents include persulfates such as ammonium persulfate and potassium persulfate; examples of reducing agents include sulfites such as sodium sulfite; and examples of transition metal salts include iron sulfate (Ir).
), Examples of azo compounds include azobisisobutyronitrile, and examples of organic peroxides include iso-butyryl peroxide, occunoyl peroxide, di-iso-propyl peroxy-di-carbonate. etc.
本発明の含フツ素共重合体は、フッ素ゴム、成形材料等
種々の用途があるが、該共重合体に硬化剤を配合し、常
温硬化型フッ素樹脂塗料として用いるのが特に有用であ
る。酸共重合体を常温硬化型フッ素樹脂塗料に用いる場
合、該共重合体は、１．１−ジフルオロエチレン５０〜
９９モル％、前記式で表わされる官能基を含有する単量
体１〜５０モル％および前記式で表わされるフルオロオ
レフィン３０モル％以下を共重合したものであるのが好
ましい、１，１−ジフルオロエチレン含有攪が５０モル
％以上であると塗料皮膜の耐薬品性、耐候性、耐汚染性
等が良好であり、官能基を含有する単量体が１〜５０モ
ル％含有されていると、共重合する際の共重合性や塗料
とした時のび化性が良く、フルオロオレフィンが３０モ
ル％以下含有されていると、含フツ素共重合体の有機）
容媒に対する溶解性が良い。The fluorine-containing copolymer of the present invention has various uses such as fluororubber and molding materials, but it is particularly useful to blend the copolymer with a curing agent and use it as a room temperature-curable fluororesin paint. When the acid copolymer is used in a room-temperature curing fluororesin coating, the copolymer has 50 to 1,1-difluoroethylene.
99 mol%, 1 to 50 mol% of a monomer containing a functional group represented by the above formula, and 30 mol% or less of a fluoroolefin represented by the above formula are preferably copolymerized, 1,1-difluoro When the ethylene content is 50 mol% or more, the paint film has good chemical resistance, weather resistance, stain resistance, etc., and when the monomer containing a functional group is contained from 1 to 50 mol%, If the copolymerizability during copolymerization and spreadability when used as a paint are good, and the fluoroolefin content is 30 mol% or less, the fluorine-containing copolymer (organic)
Good solubility in the medium.
本発明の含フツ素共重合体に配合することができる硬化
剤としては、例えばヘキザメチレンジイソシアネート、
トリレンジイソシアネート、水素添加トリレンジイソシ
アネート等のイソシアネートｉがある。このイソシアネ
ート類は、該共重合中の官能基と反応（架橋）し、常温
で塗料を硬化させる１肋きを有している。Examples of curing agents that can be incorporated into the fluorine-containing copolymer of the present invention include hexamethylene diisocyanate,
Isocyanates i include tolylene diisocyanate and hydrogenated tolylene diisocyanate. This isocyanate reacts (crosslinks) with the functional group in the copolymerization and has one side that cures the paint at room temperature.
本発明の含フツ素共重合体を含有する常温硬化型フッ素
樹脂塗料は、通常の塗料と同様、屋外または屋内用の塗
料として金属、木材、コンクリート、プラスチイック等
の基材に適用することができ、耐候性、耐薬品性、耐汚
染性等を付与することができる。また、本発明の含フツ
素共重合体は、更にそのガラス転移点を低下させるＪＩ
Ｌ量体を少量含有させることにより、フッ素ゴム材料と
しても有用なものである。The room-temperature-curing fluororesin paint containing the fluorine-containing copolymer of the present invention can be applied to base materials such as metal, wood, concrete, and plastic as an outdoor or indoor paint, just like ordinary paints. It can provide weather resistance, chemical resistance, stain resistance, etc. In addition, the fluorine-containing copolymer of the present invention further has a JI which lowers its glass transition point.
By containing a small amount of L-mer, it is also useful as a fluororubber material.
次に本発明の含フツ素共重合体の調製例および通光性試
験例ならびに本発明の含フツ素共重合体を常温硬化型フ
ッ素樹脂塗料材料として使用した実施例を示す。Next, preparation examples and light transmittance test examples of the fluorine-containing copolymer of the present invention, and examples in which the fluorine-containing copolymer of the present invention are used as a room temperature-curable fluororesin coating material will be shown.
調製例１
２５０ ｃｃのオートクレーブに酢酸エチル５０ｃｃ、
ジイソプロピルパーオキシジカーボネート０．５ ｇお
よび式：
％式％（１）
で表わされる単量体４．３ｇを入れ、窒素で空間部を十
分置換したａ、１．１−ジフルオロエチレン（以下、Ｖ
ｄＦという、 ） １３．０ｇとクロロトリフルオロエ
チレン（以下、ＣＴＦＥという、 ） ６．０ ｇを仕
込んだ。Preparation Example 1 50 cc of ethyl acetate in a 250 cc autoclave,
0.5 g of diisopropyl peroxydicarbonate and 4.3 g of a monomer represented by the formula:
13.0 g of dF (hereinafter referred to as ) and 6.0 g of chlorotrifluoroethylene (hereinafter referred to as CTFE) were charged.
該オートクレーブを４０℃の恒温槽中に４８時間放置し
た。その後、得られた反応混合物を石油エーテル中にあ
け、沈澱物を減圧下に乾燥させ、本発明の含フツ素共重
合体１４．８ ｇを得た。The autoclave was left in a constant temperature bath at 40°C for 48 hours. Thereafter, the obtained reaction mixture was poured into petroleum ether, and the precipitate was dried under reduced pressure to obtain 14.8 g of the fluorine-containing copolymer of the present invention.
得られた共重合体の分子量は、ＧＰＣ分析によれば２万
〜１５万の分布を有し、メチルエチルケトン中の極限粘
度（〔η〕）は０．２２ 、示差走査熱量計（Ｄ Ｓ
Ｃ）によるガラス転移温度（Ｔｇ）は−１６℃、熱分解
温度（Ｔｄ）は３３６℃であった。The molecular weight of the obtained copolymer has a distribution of 20,000 to 150,000 according to GPC analysis, the intrinsic viscosity ([η]) in methyl ethyl ketone is 0.22, and the molecular weight distribution is 20,000 to 150,000 according to GPC analysis.
The glass transition temperature (Tg) according to C) was -16°C, and the thermal decomposition temperature (Td) was 336°C.
トリフルオロ酢酸を外部標準とするｕＦ核磁気共鳴分析
（ＮＭＲ）によれば、フン化ビニリデンに由来するＣＦ
ｔのシグナルがδ−−１０〜−２０ｐｐ−とδ−−３０
〜−３９ｐｐｍに、ＣＴＦＥに由来するＣＦ、とＣＦの
シグナルがδ＝ −４０〜−４５ｐｐ−に、単量体（１
）に由来するＣＦのシグナルがδ−−９０〜−１１０ｐ
ｐ−に観測され、赤外吸収分析によれば、０Ｈ１ＣＨお
よびＣＦｔの伸縮振動に基づく吸収帯がそれぞれ３２０
０〜３５００ｃｍ−’ 、２９００〜３０００ｃｍ−’
および１１２０〜１２８０ｃｍ−’ に観測された。According to uF nuclear magnetic resonance analysis (NMR) using trifluoroacetic acid as an external standard, CF derived from vinylidene fluoride
The signal of t is δ−10 to −20pp− and δ−30
At ~-39 ppm, the CF and CF signals originating from CTFE are at δ = -40 to -45 ppm, and the monomer (1
) The CF signal derived from δ−90 to −110p
p-, and according to infrared absorption analysis, the absorption bands based on the stretching vibrations of 0H1CH and CFt are 320, respectively.
0~3500cm-', 2900~3000cm-'
and was observed at 1120-1280 cm-'.
前記’ ９Ｆ −Ｎ Ｍ Ｒおよび元素分析より、前記
得られた共重合体は、ＶｄＦ／単量体（１）／ＣＴＦＥ
＝７／２／１ （モル）の共重合体であった。From the above '9F-NMR and elemental analysis, it was found that the obtained copolymer was composed of VdF/monomer (1)/CTFE.
=7/2/1 (mol) copolymer.
調製例２〜４
第１表に示す各単量体を用い、調製例１と同様の条件で
本発明の含フツ素共重合体を調製した。Preparation Examples 2 to 4 Fluorine-containing copolymers of the present invention were prepared using the monomers shown in Table 1 under the same conditions as Preparation Example 1.
分析も調製例１と同様のことを行った。結果を第１表に
示す。The analysis was also carried out in the same manner as in Preparation Example 1. The results are shown in Table 1.
調製例５
ｖａ Ｆ ２６．３ ｇ、 ＣＴＦＥ ２．５ｇおよび
式：％式％（４）
で表わされる単量体８．９ｇを使用した他は調製例１と
同じ手順で共重合体を調製した。共重合体組成は、Ｖｄ
Ｆ／填量体（４） ／ ＣＴ Ｆ Ｅ ＝８２／ １．
１／７（モル）、〔η）、ＴｇおよびＴｄは、それぞれ
０．１５、−１３℃および２８０℃であった。Preparation Example 5 A copolymer was prepared using the same procedure as Preparation Example 1, except that 26.3 g of va F, 2.5 g of CTFE, and 8.9 g of a monomer represented by the formula % formula % (4) were used. . The copolymer composition is Vd
F/filler (4)/CTFE=82/1.
1/7 (mol), [η), Tg and Td were 0.15, -13°C and 280°C, respectively.
五周製例６
ＶｄＦ １２．５ ｇＳＣＴＦＥ ３．０ｇおよび式：
で表わされる単量体３．４ｇを使用した他は調製例１と
同じ手順で共重合を調製した。共重合体組成は、ＶｄＦ
／単量体（５）／ＣＴＦＥ−８０／８／１２（モル）、
（η）、ＴｇおよびＴｄは、それぞれ０．１日、−１９
℃および２９０℃であった。Five rounds production example 6 VdF 12.5 g SCTFE 3.0 g and formula:
Copolymerization was prepared in the same manner as in Preparation Example 1 except that 3.4 g of the monomer represented by was used. The copolymer composition is VdF
/monomer (5)/CTFE-80/8/12 (mol),
(η), Tg and Td are 0.1 day and −19, respectively.
℃ and 290℃.
調製例７
１０００ ｃｃのオートクレーブに水２５０ｃｃ、 １
．２−ジクロロ−１，１，２，２−テトラフルオロエタ
ン２５０ｃｃおよび単量体（１） １５．１ ｇを仕
込み、窒素で空間部を十分置換した後、ＶｄＦ３４ｇお
よびＣＴＦＥ３゜５ｇを仕込んだ、オートクレーブを４
０℃に加熱し、十分攪拌した後イソブチリルパーオキシ
ド１ｇを仕込み重合を開始した。Preparation Example 7 250 cc of water in a 1000 cc autoclave, 1
．． An autoclave was charged with 250 cc of 2-dichloro-1,1,2,2-tetrafluoroethane and 15.1 g of monomer (1), and after the space was sufficiently replaced with nitrogen, 34 g of VdF and 3.5 g of CTFE were charged. 4
After heating to 0° C. and stirring thoroughly, 1 g of isobutyryl peroxide was added to start polymerization.
重合圧力が８．５ｋｇ／ｃｍ！Ｇの一定になるように■
ｄＦ／ＣＴＦＥ−９／１ （モル）の混合ガスを供給
しながら重合を２４時間継続した。Polymerization pressure is 8.5kg/cm! So that G remains constant■
Polymerization was continued for 24 hours while supplying a mixed gas of dF/CTFE-9/1 (mol).
生成した共重合体を分離し、８０℃で減圧乾燥を行った
。得量は、８５ｇであった。The produced copolymer was separated and dried under reduced pressure at 80°C. The yield was 85g.
共重合体組成は、ＶｄＦ／単量体（１）／ＣＴＦＥ −
９１／１１／８ （モル）で、分子量分布、Ｔｇおよ
びＴｄはそれぞれ２万〜２０万、−２１℃および３４１
℃であった。The copolymer composition is VdF/monomer (1)/CTFE −
91/11/8 (mol), molecular weight distribution, Tg and Td are 20,000 to 200,000, -21℃ and 341, respectively.
It was ℃.
調製例８
１０００ ｃｃのオートクレーブに水２５０ｃｃ、 １
．２−ジクロロ−１，１，２，２−テトラフルオロエタ
ン２５０ｃｃおよびｊＩＬ量体（１） ９．０ ｇを
仕込み、窒素で空間部を十分置換した後、ＶｄＦ３１ｇ
およびヘキサフルオロプロペン（ＲＦ Ｐ） １３．０
ｇを仕込んだ、オートクレーブを４０℃に加熱し、十分
攪拌した後イソブチリルパーオキシド１ｇを仕込み重合
を開始した。Preparation Example 8 250 cc of water in a 1000 cc autoclave, 1
．． Charge 250 cc of 2-dichloro-1,1,2,2-tetrafluoroethane and 9.0 g of jIL polymer (1), and after sufficiently replacing the space with nitrogen, add 31 g of VdF.
and hexafluoropropene (RF P) 13.0
After heating the autoclave to 40° C. and stirring thoroughly, 1 g of isobutyryl peroxide was charged to start polymerization.
重合圧力が８．０ｋ（７ｃｍ”Ｇの一定になるようにＶ
ｄＦ／ＨＦＰ−９２／８ （モル）の混合ガスを供給し
ながら、重合を２５時間行った。V so that the polymerization pressure is constant at 8.0k (7cm"G)
Polymerization was carried out for 25 hours while supplying a mixed gas of dF/HFP-92/8 (mol).
生成した重合体を分離し、８０℃で減圧乾燥を行った。The produced polymer was separated and dried under reduced pressure at 80°C.
得量は、８０ｇであった。The yield was 80g.
得られた共重合体のＧＰＣによる分子量は２万〜２０万
、Ｔｇは一２８℃、Ｔｄは３０２℃、融点（Ｔｍ）は１
０３℃であった。共重合体組成は、ＶｄＦ／単量体（１
）／ＲＦＰ−９０／２／８ （モル）であった。The molecular weight of the obtained copolymer by GPC is 20,000 to 200,000, Tg is -28°C, Td is 302°C, and melting point (Tm) is 1.
The temperature was 0.3°C. The copolymer composition was VdF/monomer (1
)/RFP-90/2/8 (mol).
前記調製例１〜６は、本発明の含フツ素共重合体を溶液
重合により調製した例である。一般にフルオロオレフィ
ンは、溶液重合で重合を試みても重合速度が遅く、特に
炭化水素系溶媒を用いた場合、全く重合しないことがあ
り、たとえ重合したとしてもその重合体は溶媒に対する
溶解性が悪く、従来フルオロオレフィンは、はとんど溶
液重合で重合することができなかった。Preparation Examples 1 to 6 are examples in which the fluorine-containing copolymer of the present invention was prepared by solution polymerization. In general, even if fluoroolefins are attempted to be polymerized by solution polymerization, the polymerization rate is slow, and especially if a hydrocarbon solvent is used, they may not polymerize at all, and even if they do polymerize, the polymer has poor solubility in the solvent. Conventionally, fluoroolefins could not be polymerized by solution polymerization.
前記調製例１〜６の製法によれば、容易に前記単量体を
用い含フツ素共重合体を調製することができ、従来はと
んど不可能であったフルオロオレフィンの溶液重合が可
能になった。According to the production methods of Preparation Examples 1 to 6, fluorine-containing copolymers can be easily prepared using the monomers, and solution polymerization of fluoroolefins, which was previously impossible, is possible. Became.
懸濁重合や乳化重合で調製した共重合体は、単離・乾燥
後溶媒に溶解して常温硬化型フッ素樹脂塗料として使用
することができる。A copolymer prepared by suspension polymerization or emulsion polymerization can be isolated and dried, then dissolved in a solvent and used as a room temperature-curing fluororesin paint.
第１表
（注）表中、（１）は前記と同じ、（２）は式：ＣＦｔ
＝ＣＦＣＨｚＣＨｔＯＨで表わされる単量体、（３）は
式： ＣＦＰＣＦＣＦｚＣＦｔＣＨ，ｔｃＨｘ。Table 1 (Note) In the table, (1) is the same as above, (2) is the formula: CFt
Monomer represented by =CFCHzCHtOH, (3) has the formula: CFPCFCFzCFtCH,tcHx.
Ｈで表わされる単量体を示す。A monomer represented by H is shown.
透光性試験
調製例１〜４で得た共重合体（０，２ｓ＋ｍ厚のフィル
ム）について下記の各波長での透光率を測定した。結果
を第２表に示す。Light Transmittance Test The light transmittance of the copolymers (0.2 s+m thick films) obtained in Preparation Examples 1 to 4 was measured at each of the following wavelengths. The results are shown in Table 2.
第２表
実施例１〜５
調製例１．２．５．７および８で得られた本発明の含フ
ツ素共重合体各々１００重量部をメチルイソブチルケト
ン１００ ！ｔｆｆｉ部に溶解し、得られた溶液にヘキ
サメチレンジイソシアネート三量体（硬化剤）を各々２
５重量部、２２重量部、２５重量部、１６重置部および
５重量部加え、よく混合した（順に実施例１〜５に対応
）。Table 2 Examples 1 to 5 100 parts by weight of each of the fluorine-containing copolymers of the present invention obtained in Preparation Examples 1, 2, 5, 7 and 8 were added to 100 parts by weight of methyl isobutyl ketone! tffi part, and in the resulting solution were added 2 each of hexamethylene diisocyanate trimer (curing agent).
5 parts by weight, 22 parts by weight, 25 parts by weight, 16 parts by weight and 5 parts by weight were added and mixed well (corresponding to Examples 1 to 5 in this order).
得られた各溶液を十分に脱脂した厚さ０．２１のアルミ
ニウム板に塗布し、室温で７日間乾燥させた。Each of the obtained solutions was applied to a thoroughly degreased aluminum plate with a thickness of 0.21 mm, and dried at room temperature for 7 days.
乾燥後の塗膜を肉眼で観察したところ、いずれも透明性
は良好であり、鉛筆硬度も２Ｈ以上であった。When the dried coating films were observed with the naked eye, they all had good transparency and a pencil hardness of 2H or higher.
実施例６
調製例６で得られた本発明の含フッ素共重合体１０ｏｎ
量部を各々メチルイソブチルケトン１００重量部に溶解
し、更にジエチレントリアミン（硬化剤）２５重量部を
加え、よく混合した
得られた溶液を十分に脱脂した厚さ０．２ｍ＋ｗのアル
ミニウム仮に塗布し、室温で７日間乾燥させた。乾燥後
のｆ！！膜を肉眼で観察したところ、透明性は良好であ
り、鉛筆硬度も２Ｈ以上であった。Example 6 10 on of the fluorine-containing copolymer of the present invention obtained in Preparation Example 6
Each part was dissolved in 100 parts by weight of methyl isobutyl ketone, further 25 parts by weight of diethylene triamine (hardening agent) was added, and the resulting well-mixed solution was temporarily coated on well-degreased aluminum to a thickness of 0.2 m+w and kept at room temperature. It was dried for 7 days. f after drying! ! When the film was observed with the naked eye, it was found to have good transparency and a pencil hardness of 2H or higher.
〔発明の効果〕
従来、耐候性を有する常温硬化性塗料用材料として、フ
ルオロオレフィン、シクロヘキシルビニルエーテル等を
主成分とする共重合体が知られているが、この共重合体
は、塗料の透光性を向上させるためによく使用されるメ
チルメタクリレート系重合体と相溶性が良くなかつた０
本発明の含フツ素共重合体は、これを改良したもので、
メチルメタクリレート系重合体と溶媒の有無に関係なく
相溶性が良く、共重合体自身も優れた透光性を有してい
る。[Effect of the invention] Copolymers containing fluoroolefins, cyclohexyl vinyl ether, etc. as main components have been known as weather-resistant room-temperature-curing paint materials. It has poor compatibility with methyl methacrylate polymers, which are often used to improve properties.
The fluorine-containing copolymer of the present invention is an improved version of this,
It has good compatibility with the methyl methacrylate polymer regardless of the presence or absence of a solvent, and the copolymer itself has excellent translucency.
以上that's all
Claims (1)
▼または −ＣＯＯＨ基、ｍは０または１〜１０の整数、ｎは１〜
４の整数を示す。） で表わされる構造単位１〜５０モル％および式： −ＣＦ＿２−ＣＦＹ−（ｃ） （式中、Ｙは塩素、フッ素またはトリフルオロメチル基
を示す。） で表わされる構造単位３０モル％以下（ただし、構造単
位（ａ）、（ｂ）および（ｃ）の合計は１００モル％で
ある。）から本質的に構成される、分子量１０，０００
〜５００，０００の含フッ素ランダム共重合体。[Claims] 1. 50 to 99 mol% of structural units represented by the formula: -CH_2-CF_2-(a), Formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼(b) (In the formula, X is -OH, ▲Mathematical formulas, chemical formulas, tables, etc.▼ or -COOH group, m is 0 or an integer from 1 to 10, n is 1 to
Indicates an integer of 4. ) and 30 mol% or less of structural units represented by the formula: -CF_2-CFY-(c) (wherein, Y represents chlorine, fluorine or trifluoromethyl group) ( However, the total of structural units (a), (b) and (c) is 100 mol%), with a molecular weight of 10,000
~500,000 fluorine-containing random copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16824887A JPS6354409A (en) | 1987-07-06 | 1987-07-06 | Fluorinated copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16824887A JPS6354409A (en) | 1987-07-06 | 1987-07-06 | Fluorinated copolymer |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58175123A Division JPS6067517A (en) | 1983-09-21 | 1983-09-21 | Fluorine-contained copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6354409A true JPS6354409A (en) | 1988-03-08 |
| JPH0257085B2 JPH0257085B2 (en) | 1990-12-04 |
Family
ID=15864500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16824887A Granted JPS6354409A (en) | 1987-07-06 | 1987-07-06 | Fluorinated copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6354409A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997015623A1 (en) * | 1995-10-27 | 1997-05-01 | Daikin Industries, Ltd. | Resin composition, molding produced using the same, and process for producing the same |
| WO1997048774A1 (en) * | 1996-06-19 | 1997-12-24 | Daikin Industries, Ltd. | Coating composition, coating film, and process for the production of the film |
| WO2000011093A1 (en) * | 1998-08-24 | 2000-03-02 | Daikin Industries, Ltd. | Thin coating film made of fluoropolymer and method of forming the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU686814B2 (en) * | 1994-06-09 | 1998-02-12 | Daikin Industries, Ltd. | Fluoroolefin, fluoropolymer, and thermoplastic resin composition containing the polymer |
-
1987
- 1987-07-06 JP JP16824887A patent/JPS6354409A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997015623A1 (en) * | 1995-10-27 | 1997-05-01 | Daikin Industries, Ltd. | Resin composition, molding produced using the same, and process for producing the same |
| US6479578B2 (en) | 1995-10-27 | 2002-11-12 | Daikin Industries, Ltd. | Resin composition |
| WO1997048774A1 (en) * | 1996-06-19 | 1997-12-24 | Daikin Industries, Ltd. | Coating composition, coating film, and process for the production of the film |
| US6207236B1 (en) | 1996-06-19 | 2001-03-27 | Daikin Industries, Ltd. | Coating composition, coating film, and method for producing coating film |
| WO2000011093A1 (en) * | 1998-08-24 | 2000-03-02 | Daikin Industries, Ltd. | Thin coating film made of fluoropolymer and method of forming the same |
| US6794027B1 (en) | 1998-08-24 | 2004-09-21 | Daikin Industries, Ltd. | Thin coating film comprising fluorine-containing polymer and method of forming same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0257085B2 (en) | 1990-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4544720A (en) | Fluorine-containing copolymer | |
| JPH0440365B2 (en) | ||
| JPS61275311A (en) | Curable fluoroolefin copolymer and its production | |
| US4877839A (en) | Fluorocopolymer compositions | |
| US3449305A (en) | Interpolymers of vinylidene fluoride | |
| JPH05404B2 (en) | ||
| EP0121934B1 (en) | Fluorine-containing copolymer and composition containing the same | |
| JPS61176620A (en) | Fluorine-containing copolymer | |
| JPS62250016A (en) | Fluorine-containing copolymer | |
| JPH07119260B2 (en) | Fluorine-containing copolymer | |
| JPH0320311A (en) | Curable fluurinated copolymers, their manu facture and use with varnish and paint | |
| JPS6354409A (en) | Fluorinated copolymer | |
| US4622364A (en) | Fluorine-containing copolymer and composition containing the same | |
| JPH0453808A (en) | Fluorocopolymer | |
| JP3131985B2 (en) | Fluorine-containing copolymer and coating composition containing the polymer | |
| JPH0134460B2 (en) | ||
| JP3087286B2 (en) | Vinylidene fluoride copolymer and curing composition containing it | |
| JP2746412B2 (en) | Fluorine-containing resin for paint | |
| JPS62174213A (en) | Fluorine-containing copolymer and fluororesin paint | |
| EP0570762A1 (en) | Fluoroelastomeric and fluoroplastomeric copolymers having a high resistance to bases | |
| JPS6331487B2 (en) | ||
| JPH02605A (en) | Fluorinated copolymer | |
| JPH03294312A (en) | Fluorine-containing copolymer | |
| JPH04318082A (en) | Fluorine-containing copolymer for paint | |
| JPH03139580A (en) | Coating composition |