JPH07216020A - Production of fluorine-containing copolymer containing carboxyl group - Google Patents
Production of fluorine-containing copolymer containing carboxyl groupInfo
- Publication number
- JPH07216020A JPH07216020A JP953094A JP953094A JPH07216020A JP H07216020 A JPH07216020 A JP H07216020A JP 953094 A JP953094 A JP 953094A JP 953094 A JP953094 A JP 953094A JP H07216020 A JPH07216020 A JP H07216020A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyl group
- group bonded
- fluorine
- carbon
- tertiary
- 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.)
- Pending
Links
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
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明はカルボン酸基含有含フッ
素共重合体の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a process for producing a carboxylic acid group-containing fluorocopolymer.
【0002】[0002]
【従来の技術】従来、高分子物質に酸無水物・酸イミド
化合物を導入し、接着性・高分子反応性・染色性・顔料
親和性・イオン交換性等の向上・導入を図る例が多くみ
られ、一般の高分子物質については工業化の例は多い。2. Description of the Related Art Conventionally, there are many cases in which an acid anhydride / acid imide compound is introduced into a polymer substance to improve / introduce adhesiveness, polymer reactivity, dyeability, pigment affinity, ion exchangeability, etc. There are many examples of industrialization of general polymer substances.
【0003】一方、カルボン酸基含有含フッ素共重合体
の製造方法として水酸基含有含フッ素共重合体に有機媒
体中で二塩基酸無水物を反応させ、水酸基の少なくとも
一部をカルボン酸含有エステル基に変換せしめる方法が
提案されている。On the other hand, as a method for producing a carboxylic acid group-containing fluorine-containing copolymer, a hydroxyl group-containing fluorine-containing copolymer is reacted with a dibasic acid anhydride in an organic medium so that at least a part of the hydroxyl groups is a carboxylic acid-containing ester group. The method of converting into is proposed.
【0004】[0004]
【発明が解決しようとする課題】この方法では、水酸基
含有含フッ素共重合体の水酸基が1級の炭素に結合して
いるため生成するエステル構造に加水分解の懸念がある
という問題があった。This method has a problem in that the hydroxyl group of the hydroxyl group-containing fluorocopolymer is bonded to the primary carbon, so that the ester structure produced may be hydrolyzed.
【0005】[0005]
【課題を解決するための手段】本発明は前記問題点を解
決すべくなされたものであり、2級または3級炭素に結
合する水酸基を有する水酸基含有含フッ素共重合体に二
塩基酸の酸無水物を反応させることを特徴とするカルボ
キシル基含有含フッ素共重合体の製造方法である。SUMMARY OF THE INVENTION The present invention has been made to solve the above-described problems, and a hydroxyl group-containing fluorocopolymer having a hydroxyl group bonded to a secondary or tertiary carbon is added to a dibasic acid. A method for producing a carboxyl group-containing fluorocopolymer, which comprises reacting an anhydride.
【0006】本発明において2級または3級炭素に結合
する水酸基を有する水酸基含有含フッ素共重合体の製造
は、2級または3級炭素に結合する水酸基を有する単量
体とエチレン性不飽和結合を有する単量体とを共重合さ
せる方法(1)、1級炭素に結合する水酸基を有する単
量体とエチレン性不飽和結合を有する単量体を共重合さ
せたあとに、このものを2級または3級炭素に結合する
水酸基に変換する方法(2)、または1級炭素に結合す
る水酸基を有する単量体の1級炭素を2級または3級炭
素に結合する水酸基に変換して得られる単量体とエチレ
ン性不飽和結合を有する単量体を共重合させる方法
(3)が挙げられる。In the present invention, a fluorine-containing copolymer containing a hydroxyl group having a hydroxyl group bonded to a secondary or tertiary carbon is produced by a monomer having a hydroxyl group bonded to a secondary or tertiary carbon and an ethylenically unsaturated bond. (1) Copolymerizing a monomer having a hydroxyl group bonded to a primary carbon and a monomer having an ethylenically unsaturated bond, and then subjecting this to 2 Method (2) of converting to a hydroxyl group bonded to a primary or tertiary carbon, or converting a primary carbon of a monomer having a hydroxyl group bonded to a primary carbon into a hydroxyl group bonded to a secondary or tertiary carbon A method (3) of copolymerizing the monomer to be used with a monomer having an ethylenically unsaturated bond can be mentioned.
【0007】1級炭素に結合する水酸基を2級または3
級炭素に結合する水酸基に変換する方法としては、1級
炭素に結合する水酸基にプロピレンオキシド、イソブチ
レンオキシド、シクロヘキセンオキシド等のエポキシド
類を反応させる方法が挙げられる。The hydroxyl group bonded to the primary carbon has a secondary or tertiary hydroxyl group.
Examples of the method of converting to a hydroxyl group bonded to a primary carbon include a method of reacting a hydroxyl group bonded to a primary carbon with an epoxide such as propylene oxide, isobutylene oxide, or cyclohexene oxide.
【0008】2級または3級炭素に結合する水酸基を有
する単量体はシクロヘキサンジメタノール、1,2−ブ
タンジオール、ネオペンチルグリコール、1,2−ペン
タンジオール等のジオールと前記エポキシド類を反応さ
せたものとアセチレンを反応して得られるビニルエーテ
ル類、または2,5−ジメチルヘキサン−2,5−ジオ
ール等のジオールとアセチレンを反応して得られるビニ
ルエーテル類等が挙げられる。The monomer having a hydroxyl group bonded to a secondary or tertiary carbon is obtained by reacting a diol such as cyclohexanedimethanol, 1,2-butanediol, neopentyl glycol or 1,2-pentanediol with the above epoxides. And vinyl ethers obtained by reacting acetylene with acetylene, or vinyl ethers obtained by reacting diol such as 2,5-dimethylhexane-2,5-diol with acetylene.
【0009】二塩基酸の酸無水物としては、化1で表さ
れる各種化合物、具体的には無水コハク酸、無水グルタ
ル酸、無水イタコン酸、無水アジピン酸、無水1,2−
シクロヘキサンジカルボン酸、無水cis−4−シクロ
ヘキセン、1,2−ジカルボン酸、無水フタル酸、無水
1,8−ナフタル酸、無水マレイン酸等が挙げられる。
反応性を考慮すると、非芳香族系の二塩基酸の酸無水物
が好ましく、化1中のRが炭素数2〜8のアルキレン基
であるものが好ましい。As the acid anhydride of dibasic acid, various compounds represented by Chemical formula 1, specifically, succinic anhydride, glutaric anhydride, itaconic anhydride, adipic anhydride, 1,2-anhydride.
Examples thereof include cyclohexanedicarboxylic acid, cis-4-cyclohexene anhydride, 1,2-dicarboxylic acid, phthalic anhydride, 1,8-naphthalic anhydride, and maleic anhydride.
In consideration of reactivity, a non-aromatic dibasic acid anhydride is preferable, and one in which R in Chemical formula 1 is an alkylene group having 2 to 8 carbon atoms is preferable.
【0010】[0010]
【化1】 ただし、Rは2価の有機基を示す。[Chemical 1] However, R represents a divalent organic group.
【0011】エチレン性不飽和結合を有する単量体とし
ては、フルオロオレフィン類が特に好ましく、CClF=C
F2, CHCl=CF2, CCl2=CF2, CClF=CClF,CHF= CCl2, CH2=C
ClF, CCl2=CClF, CF2=CF2,CF2=CH2 等のフルオロエチレ
ン類、CF2ClCF=CF2, CF3CCl=CF2,CF3CF=CFCl, CF2ClCCl
=CF2, CF2ClCF=CFCl,CFCl2CF=CF2, CF3CCl=CClF, CF3CC
l=CCl2,CClF2CF=CCl2, CCl3CF=CF2, CF2ClCCl=CCl2, CF
Cl2CCl=CCl2, CF3CF=CHCl, CClF2CF=CHCl, CH3CCl=CHC
l, CHF2CCl=CCl2, CF2ClCH=CCl2,CF2ClCCl=CHCl,CCl3CF
=CHCl, CCl3CF=CHCl, CHBrCF=CCl2 CF2=CFOCF3、CF2=CFO
C3F7 等のフルオロプロヘン類、CF3CCl=CFCF3,CF2=CFCF
2CClF2, CF3CF2CF=CCl2等の炭素子数4以上のフルオロ
オレフィン類が挙げられる。またこれらのフルオロオレ
フィン類としては単独でもよく、複数種が併用されても
よい。As the monomer having an ethylenically unsaturated bond, fluoroolefins are particularly preferable, and CClF = C
F 2 , CHCl = CF 2 , CCl 2 = CF 2 , CClF = CClF, CHF = CCl 2 , CH 2 = C
Fluoroethylenes such as ClF, CCl 2 = CClF, CF 2 = CF 2 , CF 2 = CH 2 , CF 2 ClCF = CF 2 , CF 3 CCl = CF 2 , CF 3 CF = CFCl, CF 2 ClCCl
= CF 2 , CF 2 Cl CF = CFCl, CFCl 2 CF = CF 2 , CF 3 CCl = CClF, CF 3 CC
l = CCl 2 , CClF 2 CF = CCl 2 , CCl 3 CF = CF 2 , CF 2 ClCCl = CCl 2 , CF
Cl 2 CCl = CCl 2 , CF 3 CF = CHCl, CClF 2 CF = CHCl, CH 3 CCl = CHC
l, CHF 2 CCl = CCl 2 , CF 2 ClCH = CCl 2 , CF 2 ClCCl = CHCl, CCl 3 CF
= CHCl, CCl 3 CF = CHCl , CHBrCF = CCl 2 CF 2 = CFOCF 3, CF 2 = CFO
Fluoroprohens such as C 3 F 7 , CF 3 CCl = CFCF 3 , CF 2 = CFCF
2 CClF 2, CF 3 CF 2 CF = CCl 4 or more of the fluoroolefins Tansoko such 2. These fluoroolefins may be used alone or in combination of two or more.
【0012】カルボキシル基含有含フッ素共重合体中の
フルオロオレフィン類の共重合割合は20〜80モル
%、好ましくは30〜70モル%である。水酸基を有す
る単量体の共重合割合は5〜70モル%、好ましくは1
0〜60モル%である。The copolymerization ratio of fluoroolefins in the carboxyl group-containing fluorocopolymer is 20 to 80 mol%, preferably 30 to 70 mol%. The copolymerization ratio of the monomer having a hydroxyl group is 5 to 70 mol%, preferably 1
It is 0 to 60 mol%.
【0013】またカルボキシル基含有含フッ素共重合体
にその特徴を失わない範囲で共重合可能な他の単量体を
1〜40モル%の割合で共重合させることができる。以
下の単量体が例示可能である。Further, another monomer copolymerizable with the carboxyl group-containing fluorine-containing copolymer can be copolymerized in a proportion of 1 to 40 mol% within a range not losing its characteristics. The following monomers can be exemplified.
【0014】エチレン、プロピレン、イソブチレン等の
オレフィン類、塩化ビニル、塩化ビニリデン等のハロオ
レフィン類、酢酸ビニル、酪酸ビニル、ピバリン酸ビニ
ル、安息香酸ビニル、バーサチック酸ビニル等のカルボ
ン酸ビニル類、エチルビニルエーテル、n−ブチルビニ
ルエーテル、オクチルビニルエーテル、ネオペンチルビ
ニルエーテル、シクロヘキシルビニルエーテル等のアル
キルビニルエーテル類、フェニルビニルエーテル、ベン
ジルビニルエーテル、ナフチルビニルエーテル等の芳香
族ビニルエーテル類、メチルイソプロペニルエーテル、
プロピルイソプロペニルエーテル等のイソプロペニルエ
ーテル類、ギ酸アリル、酪酸アリル、安息香酸アリル、
シクロヘキサンカルボン酸アリル等のカルボン酸アリル
類、アリルエチルエーテル、アリルフェニルエーテル等
のアリルエーテル類、アクリル酸エチル、メタクリル酸
メチル等の(メタ)アクリル酸エステル類等が挙げられ
る。Olefins such as ethylene, propylene and isobutylene, haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl butyrate, vinyl pivalate, vinyl benzoate, vinyl carboxylates such as vinyl versatate and ethyl vinyl ether. Alkyl vinyl ethers such as n-butyl vinyl ether, octyl vinyl ether, neopentyl vinyl ether and cyclohexyl vinyl ether, aromatic vinyl ethers such as phenyl vinyl ether, benzyl vinyl ether and naphthyl vinyl ether, methyl isopropenyl ether,
Isopropenyl ethers such as propyl isopropenyl ether, allyl formate, allyl butyrate, allyl benzoate,
Examples thereof include allyl carboxylates such as allyl cyclohexanecarboxylate, allyl ethers such as allyl ethyl ether and allyl phenyl ether, and (meth) acrylic acid esters such as ethyl acrylate and methyl methacrylate.
【0015】本発明のカルボキシル基含有含フッ素共重
合体は、数平均分子量が2,000〜100,000、
好ましくは、6,000〜30,000でかつ分子量分
布が4.0以下、好ましくは3.0以下のものが好適で
ある。分子量が2,000未満では耐候性、耐薬品性が
劣り、1,000〜100,000を超えると塗料粘度
が高く、施工性に難点がある。分子量分布が4を超える
と同様に施工性に難点が現われる。The carboxyl group-containing fluorocopolymer of the present invention has a number average molecular weight of 2,000 to 100,000,
It is preferably 6,000 to 30,000 and has a molecular weight distribution of 4.0 or less, preferably 3.0 or less. If the molecular weight is less than 2,000, the weather resistance and chemical resistance are inferior, and if it exceeds 1,000 to 100,000, the viscosity of the coating material is high, and there is a problem in workability. When the molecular weight distribution is more than 4, the workability also suffers.
【0016】本発明のカルボキシル基含有含フッ素共重
合体は、所定割合の単量体混合物に重合触媒の共存下、
あるいは非共存下に、重合開始剤あるいは電離性放射線
などの重合開始源を作用せしめて共重合反応を行わせる
ことによって製造できる。The carboxyl group-containing fluorocopolymer of the present invention is prepared by coexisting a monomer mixture in a predetermined ratio with a polymerization catalyst,
Alternatively, it can be produced by allowing a polymerization initiator or a polymerization initiation source such as ionizing radiation to act in the absence of coexistence to cause a copolymerization reaction.
【0017】ここで、重合開始剤としては、重合形式あ
るいは重合媒体に応じて、水溶性のものあるいは油溶性
のものが適宜使用可能である。As the polymerization initiator, a water-soluble one or an oil-soluble one can be appropriately used depending on the type of polymerization or the polymerization medium.
【0018】水溶性開始剤としては、過硫酸カリウムの
ような過硫酸塩、過酸化水素またはこれらと亜硫酸水素
ナトリウム、チオ硫酸ナトリウムのような還元剤からな
るレドックス開始剤、さらにはこれらに少量の鉄、第一
鉄塩、硝酸銀等を共存させた系等の無機系開始剤、また
はジコハク酸パーオキシド、ジグルタール酸パーオキシ
ド、モノコハク酸パーオキシドのような二塩基酸酸化
物、アゾビスイソブチルアミジン二塩基酸塩等の有機系
開始剤が例示される。The water-soluble initiator may be a persulfate such as potassium persulfate, hydrogen peroxide or a redox initiator composed of hydrogen peroxide or a reducing agent such as sodium bisulfite or sodium thiosulfate, and a small amount of them. Inorganic initiators such as those containing iron, ferrous salt, silver nitrate, etc., or dibasic acid oxides such as disuccinic acid peroxide, diglutaric acid peroxide, monosuccinic acid peroxide, azobisisobutylamidine dibasic acid salt Organic initiators such as
【0019】また、油溶性開始剤としては、t−ブチル
パーオキシアセテートのようなパーオキシエステル型過
酸化物、ジイソプロピルパーオキシジカーボネートのよ
うなジアルキルパーオキシジカーボネート、ベンゾイル
パーオキシド、アゾビスイソブチロニトリル等が例示さ
れる。As the oil-soluble initiator, peroxyester type peroxides such as t-butylperoxyacetate, dialkylperoxydicarbonates such as diisopropylperoxydicarbonate, benzoyl peroxide, azobisisocarbonate. Butyronitrile and the like are exemplified.
【0020】重合開始剤の使用量は、種類、共重合反応
条件に応じて適宜変更可能であるが、通常は共重合され
るべき単量体全量に対して、0.05〜0.5重量%程
度が採用される。The amount of the polymerization initiator used can be appropriately changed according to the type and the conditions of the copolymerization reaction, but usually 0.05 to 0.5% by weight based on the total amount of the monomers to be copolymerized. % Is used.
【0021】上記共重合反応に際して、反応形式として
は特に限定されることはなく、塊状重合、懸濁重合、乳
化重合、溶液重合等が採用しうるが、重合操作の安定
性、生成共重合体の分離の容易性等から、水性媒体中で
の乳化重合あるいはt−ブタノール等のアルコール類、
エステル類、1個以上のフッ素原子を含む飽和ハロゲン
化炭化水素類、キシレン等の芳香族炭化水素等を溶媒と
する溶液重合等が好ましい。反応温度は10℃〜90℃
程度が採用され、反応圧力は、適宜選定可能であるが、
通常は、0〜100kg/cm2 G、特に、0〜50k
g/cm2 G程度を採用するのが望ましい。In the above copolymerization reaction, the reaction mode is not particularly limited, and bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization and the like can be adopted, but the stability of the polymerization operation, the copolymer produced. From the standpoint of ease of separation, etc., emulsion polymerization in an aqueous medium or alcohols such as t-butanol,
Solution polymerization using an ester, a saturated halogenated hydrocarbon containing one or more fluorine atoms, an aromatic hydrocarbon such as xylene, etc. as a solvent is preferable. Reaction temperature is 10 ° C to 90 ° C
The degree is adopted, and the reaction pressure can be appropriately selected,
Usually 0 to 100 kg / cm 2 G, especially 0 to 50 k
It is desirable to adopt g / cm 2 G or so.
【0022】本発明により得られるカルボキシル基含有
含フッ素共重合体は、特に塗料用のベース樹脂として好
ましく用いられる。この場合、共重合体の固有粘度、酸
価、水酸基価は以下で述べる範囲とすることが好まし
い。The carboxyl group-containing fluorocopolymer obtained by the present invention is preferably used as a base resin for paints. In this case, the intrinsic viscosity, acid value and hydroxyl value of the copolymer are preferably within the ranges described below.
【0023】カルボキシル基含有含フッ素共重合体の固
有粘度は0.05〜2.0dl/g程度が採用され、こ
の範囲に抑えるために、連鎖移動定数の比較的大きい反
応媒体を使用したり、適宜連鎖移動剤の共存下に共重合
反応を行わしめることが好ましい。The carboxyl group-containing fluorine-containing copolymer has an intrinsic viscosity of about 0.05 to 2.0 dl / g. In order to suppress this range, a reaction medium having a relatively large chain transfer constant is used, It is preferable to carry out the copolymerization reaction in the coexistence of a chain transfer agent as appropriate.
【0024】また、含フッ素重合体の水酸基をカルボキ
シル基に変換させる反応は、水酸基の一部を行ってもよ
いし、また全部を行ってもよい。ただし、カルボキシル
基含有含フッ素共重合体の酸価が少なくとも10mgK
OH/gとなるようにすることが好ましい。The reaction for converting the hydroxyl groups of the fluoropolymer to the carboxyl groups may be carried out either partially or entirely. However, the acid value of the carboxyl group-containing fluorocopolymer is at least 10 mgK
OH / g is preferable.
【0025】カルボキシル基の量が少なすぎる、すなわ
ち、酸価が10mgKOH/gよりも少ないものは、水
性化が難しく、また、酸価があまりに大きなものは塗膜
の耐アルカリ性、耐沸水性などが低下することがあり、
好ましくない。酸価が10〜150mgKOH/g程
度、特に10〜100mgKOH/g程度の含フッ素重
合体が好ましく採用される。When the amount of carboxyl groups is too small, that is, when the acid value is less than 10 mgKOH / g, it is difficult to make the aqueous solution, and when the acid value is too large, the coating film has poor alkali resistance and boiling water resistance. May decrease,
Not preferable. A fluorine-containing polymer having an acid value of about 10 to 150 mgKOH / g, particularly about 10 to 100 mgKOH / g is preferably adopted.
【0026】また前述の水酸基は、少なくとも一部が残
っていることが、硬化剤と反応して、耐溶剤性などに優
れた塗膜を得ることができるため好ましい。特に水酸基
を、水酸基価10〜150mgKOH/g程度の割合で
含有するものが好ましく採用される。Further, it is preferable that at least a part of the above-mentioned hydroxyl group remains because it is possible to react with the curing agent and obtain a coating film excellent in solvent resistance and the like. In particular, those containing a hydroxyl group at a hydroxyl value of about 10 to 150 mgKOH / g are preferably adopted.
【0027】また、カルボキシル基を有する含フッ素重
合体は、上記のようなフルオロオレフィンに基づく重合
した単位、カルボキシル基を有する重合した単位および
水酸基を有する重合した単位のみから構成されていても
よいし、また他の共重合可能な単量体が共重合されてい
てもよい。所望の塗膜物性(硬度、光沢、顔料分散性な
ど)に応じ、適宜アルキルビニルエーテル、アルキルア
リルエーテル、アルキルビニルエステル、アルキルアリ
ルエステル、フルオロアルキルビニルエーテルなどを共
重合させてもよい。これら単量体が共重合されている場
合においても、フルオロオレフィンに基づく重合した単
位の含有割合、酸価、水酸基価は前述の範囲内とするこ
とが好ましい。Further, the fluoropolymer having a carboxyl group may be composed of only the above-mentioned polymerized unit based on fluoroolefin, the polymerized unit having a carboxyl group and the polymerized unit having a hydroxyl group. Also, other copolymerizable monomers may be copolymerized. An alkyl vinyl ether, an alkyl allyl ether, an alkyl vinyl ester, an alkyl allyl ester, a fluoroalkyl vinyl ether, etc. may be appropriately copolymerized depending on desired physical properties of the coating film (hardness, gloss, pigment dispersibility, etc.). Even when these monomers are copolymerized, it is preferable that the content ratio of the polymerized unit based on the fluoroolefin, the acid value, and the hydroxyl value are within the above ranges.
【0028】[0028]
【実施例】以下、本発明をより具体的に説明するため実
施例を示す。なお、実施例中の部数は、特にことわりの
ない限り重量部を示す。EXAMPLES Examples will be shown below to more specifically describe the present invention. In addition, the number of parts in the examples means part by weight unless otherwise specified.
【0029】実施例1 [原料含フッ素重合体の合成]内容積200ccのステン
レス製撹拌機付オートクレーブ(耐圧50kg/cm 2
G)にクロロトリフルオロエチレン35部、エチルビニ
ルエーテル6.6部、シクロヘキシルビニルエーテル
7.8部、2,5−ジメチル−2,5−ヘキサンジオー
ルモノビニルエーテル26部、キシレン98部、エタノ
ール28部、アゾビスイソブチロニトリル0.5部、無
水炭酸カリウム1.5部を仕込み、液体窒素にて冷却し
て固化脱気により溶存空気を除去した後に、65℃で1
6時間反応を行い、水酸基含有含フッ素重合体を得た。Example 1 [Synthesis of Fluorine-Containing Polymer as Raw Material] Stainless Steel with Internal Volume of 200 cc
Less autoclave with stirrer (pressure resistance 50kg / cm 2
G) 35 parts chlorotrifluoroethylene, ethyl vinyl
6.6 parts of luether, cyclohexyl vinyl ether
7.8 parts, 2,5-dimethyl-2,5-hexanedio
26 parts of rumono vinyl ether, 98 parts of xylene, ethano
28 parts, azobisisobutyronitrile 0.5 parts, nothing
Charge 1.5 parts of potassium hydrogen carbonate and cool with liquid nitrogen.
After removing dissolved air by solidification degassing,
Reaction was carried out for 6 hours to obtain a hydroxyl group-containing fluoropolymer.
【0030】得られた水酸基含有含フッ素重合体(水酸
基価は約110mgKOH/g樹脂)の約60重量%キ
シレン溶液を90℃に加熱し、重合体100部に対して
ヘキサヒドロ無水フタル酸を7.4部加え、さらに0.
2部のトリエチルアミンを添加して、10時間反応させ
た。反応液の赤外スペクトルを測定すると、反応前に観
測された無水フタル酸の特性吸収(1850cm-1、1
780cm-1)が、反応後では消失しており、カルボン
酸(1710cm-1)およびエステル(1735c
m-1)の吸収が観測された。かくしてカルボキシル基を
導入された含フッ素重合体の酸価は40mgKOH/g
樹脂であった。得られた含フッ素重合体は、キシレン溶
媒をイソプロピルアルコール溶媒に置換し、約60重量
%の溶液とした。Approximately 60 wt% xylene solution of the obtained hydroxyl group-containing fluoropolymer (having a hydroxyl value of approximately 110 mgKOH / g resin) was heated to 90 ° C., and hexahydrophthalic anhydride was added to 100 parts of the polymer. Add 4 parts, and add 0.
2 parts of triethylamine was added and reacted for 10 hours. When the infrared spectrum of the reaction solution was measured, the characteristic absorption of phthalic anhydride observed before the reaction (1850 cm -1 , 1
780 cm −1 ) has disappeared after the reaction, and carboxylic acid (1710 cm −1 ) and ester (1735c
m −1 ) absorption was observed. Thus, the acid value of the fluoropolymer having a carboxyl group introduced is 40 mgKOH / g.
It was a resin. In the obtained fluoropolymer, the xylene solvent was replaced with an isopropyl alcohol solvent to give a solution of about 60% by weight.
【0031】次にこのフッ素重合体溶液135部に撹拌
を続けながらトリエチルアミン2.04部添加した後、
ブチルセロソルブ26部を加え、更に脱イオン水を加え
て樹脂固形分濃度10重量%の水分散液とした。Next, after adding 2.04 parts of triethylamine to 135 parts of this fluoropolymer solution while continuing stirring,
Butyl cellosolve (26 parts) was added, and deionized water was further added to obtain an aqueous dispersion having a resin solid content concentration of 10% by weight.
【0032】この水分散液を40℃の温度で2週間保持
したした後の酸価の変化(ΔAV)とpHの変化(Δp
H)を測定した。結果を表1に示す。The acid value change (ΔAV) and the pH change (Δp) after this aqueous dispersion was kept at a temperature of 40 ° C. for 2 weeks
H) was measured. The results are shown in Table 1.
【0033】実施例2〜4 水酸基含有ビニルエーテルの種類を変えて実施例1と同
様の方法で含フッ素重合体の合成および安定性試験を行
った。結果を表1に示す。Examples 2 to 4 The fluorine-containing polymer was synthesized and the stability test was conducted in the same manner as in Example 1 except that the type of hydroxyl group-containing vinyl ether was changed. The results are shown in Table 1.
【0034】実施例5 実施例1において2,5−ジメチル−2,5−ヘキサン
ジオールモノビニルエーテルの代わりに4−ヒドロキシ
ブチルビニルエーテルを用いて含フッ素重合体の合成を
行った。次に含フッ素重合体の水酸基をカリウムメトキ
シドと反応させた後イソブチレンオキシドを反応させ
た。メタノール除去、精製処理を行った後試験を行っ
た。この後実施例1と同様の方法でヘキサヒドロ無水フ
タル酸と反応させた後イソプロピル溶液を得た。試験結
果を表1に示す。Example 5 A fluorine-containing polymer was synthesized by using 4-hydroxybutyl vinyl ether instead of 2,5-dimethyl-2,5-hexanediol monovinyl ether in Example 1. Next, the hydroxyl group of the fluoropolymer was reacted with potassium methoxide and then with isobutylene oxide. The test was conducted after the removal of methanol and the purification treatment. Then, the reaction was performed with hexahydrophthalic anhydride in the same manner as in Example 1 to obtain an isopropyl solution. The test results are shown in Table 1.
【0035】比較例1 実施例5においてイソブチレンオキシドの付加反応をし
ないで酸価40mgKOH/g樹脂を有する含フッ素重
合体のイソプロピル溶液を得た。試験結果を表1に示
す。Comparative Example 1 In Example 5, an isopropyl solution of a fluoropolymer having an acid value of 40 mgKOH / g resin was obtained without addition reaction of isobutylene oxide. The test results are shown in Table 1.
【0036】[0036]
【表1】 [Table 1]
【0037】[0037]
【発明の効果】本発明の樹脂は水に分散した場合の液安
定性に優れ、電着塗料などの水性塗料のベース樹脂とし
て使用した時に経時安定性が良好となる。INDUSTRIAL APPLICABILITY The resin of the present invention has excellent liquid stability when dispersed in water, and has good temporal stability when used as a base resin for aqueous paints such as electrodeposition paints.
Claims (6)
する水酸基含有含フッ素共重合体に二塩基酸の酸無水物
を反応させることを特徴とするカルボキシル基含有含フ
ッ素共重合体の製造方法。1. A method for producing a fluorinated copolymer containing a carboxyl group, which comprises reacting an acid anhydride of a dibasic acid with a fluorinated copolymer containing a hydroxyl group having a hydroxyl group bonded to a secondary or tertiary carbon. Method.
する水酸基含有含フッ素共重合体が2級または3級炭素
に結合する水酸基を有する単量体とフルオロオレフィン
類との共重合により得られるものである請求項1の方
法。2. A hydroxyl group-containing fluorine-containing copolymer having a hydroxyl group bonded to a secondary or tertiary carbon is obtained by copolymerizing a monomer having a hydroxyl group bonded to a secondary or tertiary carbon with a fluoroolefin. The method of claim 1, which is:
する単量体が2級または3級アルコールとアセチレンと
の反応で得られるビニルエーテルである請求項2の方
法。3. The method according to claim 2, wherein the monomer having a hydroxyl group bonded to secondary or tertiary carbon is vinyl ether obtained by the reaction of secondary or tertiary alcohol and acetylene.
する水酸基含有含フッ素共重合体が、1級炭素に結合す
る水酸基を有する単量体とフルオロオレフィン類との共
重合により得られる1級炭素に結合する水酸基を有する
共重合体の1級炭素に結合する水酸基を、2級または3
級炭素に結合する水酸基に変換することにより得られる
ものである請求項1の方法。4. A fluorine-containing copolymer containing a hydroxyl group having a hydroxyl group bonded to a secondary or tertiary carbon is obtained by copolymerizing a monomer having a hydroxyl group bonded to a primary carbon and a fluoroolefin. The hydroxyl group bonded to the primary carbon of the copolymer having a hydroxyl group bonded to the primary carbon is a secondary or tertiary hydroxyl group.
The method according to claim 1, which is obtained by converting to a hydroxyl group bonded to a primary carbon.
する水酸基含有含フッ素共重合体が、1級炭素に結合す
る水酸基を有する単量体の1級炭素に結合する水酸基を
2級または3級炭素に結合する水酸基に変換することに
より得られる単量体とフルオロオレフィン類との共重合
により得られるものである請求項1の方法。5. A hydroxyl group-containing fluorocopolymer having a hydroxyl group bonded to a secondary or tertiary carbon, wherein the hydroxyl group bonded to the primary carbon of the monomer having a hydroxyl group bonded to the primary carbon is secondary or The method according to claim 1, which is obtained by copolymerizing a fluoroolefin with a monomer obtained by converting it into a hydroxyl group bonded to a tertiary carbon.
級炭素に結合する水酸基に変換する方法が1級炭素に結
合する水酸基にエポキシド類を反応させる方法である請
求項4または5の方法。6. A hydroxyl group bonded to primary carbon is secondary or tertiary.
The method according to claim 4 or 5, wherein the method of converting to a hydroxyl group bonded to a primary carbon is a method of reacting an epoxide with a hydroxyl group bonded to a primary carbon.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP953094A JPH07216020A (en) | 1994-01-31 | 1994-01-31 | Production of fluorine-containing copolymer containing carboxyl group |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP953094A JPH07216020A (en) | 1994-01-31 | 1994-01-31 | Production of fluorine-containing copolymer containing carboxyl group |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH07216020A true JPH07216020A (en) | 1995-08-15 |
Family
ID=11722829
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP953094A Pending JPH07216020A (en) | 1994-01-31 | 1994-01-31 | Production of fluorine-containing copolymer containing carboxyl group |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07216020A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1253134A1 (en) * | 2001-04-26 | 2002-10-30 | Mitsubishi Gas Chemical Company, Inc. | Vinyl-polymerizable monomer having tertiary hydroxyl group and polymer |
-
1994
- 1994-01-31 JP JP953094A patent/JPH07216020A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1253134A1 (en) * | 2001-04-26 | 2002-10-30 | Mitsubishi Gas Chemical Company, Inc. | Vinyl-polymerizable monomer having tertiary hydroxyl group and polymer |
CN100378061C (en) * | 2001-04-26 | 2008-04-02 | 三菱瓦斯化学株式会社 | Vinyl polymerized monomer and polymer contg. tert-hydroxyl |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0690880B1 (en) | Fluorine-containing polymers and preparation and use thereof | |
US7897682B2 (en) | Aqueous polymerization of fluorinated monomers using polymerization agent comprising fluoropolyether acid or salt and hydrocarbon surfactant | |
JP5128492B2 (en) | Fluorinated surfactants for producing fluoropolymers | |
US7776946B2 (en) | Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant | |
US8119750B2 (en) | Explosion taming surfactants for the production of perfluoropolymers | |
US5001278A (en) | Novel fluorovinyl ether and copolymer comprising the same | |
JP5375095B2 (en) | Method for producing perfluorocarboxylate, method for producing perfluorocarboxylate aqueous solution, method for producing homopolymer or copolymer of tetrafluoroethylene | |
EP1245596B1 (en) | Improved aqueous emulsion polymerization process for producing fluoropolymers | |
WO2018167189A1 (en) | Method for making fluoropolymers | |
US4151340A (en) | Process for producing fluorocopolymer | |
RU2265616C2 (en) | Process of polymerization of aqueous emulsions to produce fluoropolymers | |
JPH07216020A (en) | Production of fluorine-containing copolymer containing carboxyl group | |
US5654373A (en) | Peroxide curable fluororubbers containing no cure-site monomers | |
JPH08157537A (en) | Carboxylated fluorocopolymer and its production | |
EP1741729B1 (en) | Polymerization process | |
JPH06322028A (en) | Production of vinylidene fluoride polymer | |
JPH0753646A (en) | Fluorine-containing aqueous dispersion | |
JPH10279634A (en) | Production of fluorocopolymer | |
JPH05230152A (en) | Copolymer containing fluorovinyl ether | |
JPH06199958A (en) | Production of perfluorocarbon polymer having sulfonic acid-type functional group | |
JPH07238116A (en) | Carboxylated fluorocopolymer and its production | |
WO2023165912A1 (en) | Method for making fluoropolymers containing ion exchange groups | |
JPH0465404A (en) | Production of fluorine-containing polyester | |
JPH11171933A (en) | Fluorine-containing copolymer and curing composition containing the copolymer | |
JPH0757786B2 (en) | Method for producing fluorine-containing copolymer |