JP4450182B2 - Method for producing fluorine-containing (meth) acrylic acid ester polymer - Google Patents

Method for producing fluorine-containing (meth) acrylic acid ester polymer Download PDF

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JP4450182B2
JP4450182B2 JP2004101708A JP2004101708A JP4450182B2 JP 4450182 B2 JP4450182 B2 JP 4450182B2 JP 2004101708 A JP2004101708 A JP 2004101708A JP 2004101708 A JP2004101708 A JP 2004101708A JP 4450182 B2 JP4450182 B2 JP 4450182B2
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acrylic acid
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越生 堀井
裕輔 川端
俊一 平尾
昭弥 小川
孝良 許
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Description

本発明は、含フッ素(メタ)アクリル酸エステル系重合体の製造方法に関する。   The present invention relates to a method for producing a fluorine-containing (meth) acrylic acid ester polymer.

高分子の分子構造にフッ素原子を導入することにより、耐熱性、耐候性、電気特性、摺動性、耐薬品性、撥水・撥油性や機械特性が既存の炭化水素系プラスチックスよりも向上することが知られており、これまでにポリテトラフルオロエチレンやポリフッ化ビニリデンに代表されるように様々なフッ素樹脂が上市されている。ただし、現在は非常に価格が高価であることや樹脂の成形性が低いために、使用範囲が限られている状態である。   By introducing fluorine atoms into the molecular structure of the polymer, heat resistance, weather resistance, electrical properties, slidability, chemical resistance, water and oil repellency, and mechanical properties are improved over existing hydrocarbon plastics. Various fluororesins have been put on the market as represented by polytetrafluoroethylene and polyvinylidene fluoride. However, the range of use is currently limited because the price is very expensive and the moldability of the resin is low.

ところで、(メタ)アクリル酸エステル系重合体は非常に安価な汎用性樹脂であり、これを原料として用いて、特定の官能基を導入することにより新規な樹脂が得られることが既に提案されている。例えば、特開平6−240017号公報には、(メタ)アクリル酸エステル系重合体に一級アミンを反応させてイミド化する技術が開示されており、(メタ)アクリル酸エステル系重合体の耐熱性を改善するとの記載がある(特許文献1参照。)。   By the way, (meth) acrylic acid ester polymer is a very inexpensive general-purpose resin, and it has already been proposed that a novel resin can be obtained by introducing a specific functional group using this as a raw material. Yes. For example, Japanese Patent Application Laid-Open No. 6-240017 discloses a technique of imidizing a (meth) acrylic acid ester polymer by reacting a primary amine, and the heat resistance of the (meth) acrylic acid ester polymer. (Refer to Patent Document 1).

この(メタ)アクリル酸エステル系重合体にフッ素原子を導入する方法としては二通りあり、フッ素原子で置換した(メタ)アクリル単量体を重合する方法(特許文献2、特許文献3参照。)のようなモノマーから製造する方法と(メタ)アクリル酸系重合体又は(メタ)アクリル酸エステル系重合体をフッ素原子含有アミンと反応させる方法(特許文献4、特許文献5参照。)のような既存の高分子を利用する方法が提案されているが、前者の方法によれば特殊な重合設備が必要であり、後者の方法によれば高価でかつ毒性が高いフッ素原子含有アミンを使用するという問題がある。
特開平6−240017号公報 特公昭55−23567号公報 特開平11−255829号公報 特開平7−118339号公報 特開平3−243609号公報
There are two methods for introducing a fluorine atom into this (meth) acrylic acid ester polymer, and a method of polymerizing a (meth) acryl monomer substituted with a fluorine atom (see Patent Document 2 and Patent Document 3). And a method of producing a monomer such as (meth) acrylic acid polymer or (meth) acrylic acid ester polymer with a fluorine atom-containing amine (see Patent Document 4 and Patent Document 5). A method using an existing polymer has been proposed, but according to the former method, a special polymerization facility is required, and according to the latter method, an expensive and highly toxic fluorine-containing amine is used. There's a problem.
JP-A-6-240017 Japanese Patent Publication No.55-23567 Japanese Patent Laid-Open No. 11-255829 Japanese Patent Laid-Open No. 7-118339 JP-A-3-243609

特殊な重合設備を使用せずに、安価に含フッ素(メタ)アクリル酸エステル系重合体を製造する手段が求められていた。   There has been a demand for means for producing a fluorine-containing (meth) acrylic acid ester polymer at a low cost without using a special polymerization facility.

上記課題を解決するため、本発明者らは鋭意研究の結果、(メタ)アクリル酸エステル系重合体とフッ素原子含有アルコールを反応させることにより、含フッ素(メタ)アクリル酸エステル系重合体を安価に製造する方法を見出し、本発明に至った。
すなわち、本発明は、(メタ)アクリル酸エステル系重合体に、下記一般式1で表されるフッ素原子含有アルコール

Figure 0004450182
(但し、Rfは少なくとも1個以上のフッ素原子を含有する炭素数1〜15のフルオロアルキル基又はフルオロアルキルエーテル基であり、nは0〜10の整数を表す。)
を反応させることを特徴とする、含フッ素(メタ)アクリル酸エステル系重合体の製造方法(請求項1)、
エステル交換触媒存在下で反応させることを特徴とする請求項1に記載の含フッ素(メタ)アクリル酸エステル系重合体の製造方法(請求項2)、
エステル交換触媒としてアルカリ金属炭酸塩、アルカリ土類金属炭酸塩、アルカリ金属重炭酸塩、アルカリ金属水酸化物から選ばれる少なくとも1種からなるエステル交換触媒を用いることを特徴とする請求項2に記載の含フッ素(メタ)アクリル酸エステル系重合体の製造方法(請求項3)、
エステル交換触媒としてルイス酸、プロトン酸から選ばれる少なくとも1種からなるエステル交換触媒を用いることを特徴とする請求項2に記載の含フッ素(メタ)アクリル酸エステル系重合体の製造方法(請求項4)、
ルイス酸としてバナジウム系化合物、チタン系化合物、ジルコニウム系化合物、ハフニウム系化合物から選ばれる少なくとも1種からなるエステル交換触媒を用いることを特徴とする請求項4に記載の含フッ素(メタ)アクリル酸エステル系重合体の製造方法(請求項5)、に関する。 In order to solve the above-mentioned problems, the present inventors have conducted intensive research and have made a low-cost fluorinated (meth) acrylate polymer by reacting a (meth) acrylate polymer with a fluorine atom-containing alcohol. Thus, the inventors have found a method for producing the present invention and have arrived at the present invention.
That is, the present invention relates to a (meth) acrylic acid ester polymer and a fluorine atom-containing alcohol represented by the following general formula 1.
Figure 0004450182
(However, Rf is a C1-C15 fluoroalkyl group or fluoroalkyl ether group containing at least one fluorine atom, and n represents an integer of 0-10.)
A process for producing a fluorine-containing (meth) acrylic acid ester-based polymer (Claim 1),
The method for producing a fluorine-containing (meth) acrylic acid ester polymer according to claim 1, wherein the reaction is carried out in the presence of a transesterification catalyst (claim 2),
3. The transesterification catalyst comprising at least one selected from alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides is used as the transesterification catalyst. A method for producing a fluorine-containing (meth) acrylic acid ester polymer (claim 3),
The method for producing a fluorinated (meth) acrylic acid ester polymer according to claim 2, wherein the transesterification catalyst comprises at least one transesterification catalyst selected from a Lewis acid and a protonic acid. 4),
The fluorine-containing (meth) acrylic acid ester according to claim 4, wherein a transesterification catalyst comprising at least one selected from a vanadium compound, a titanium compound, a zirconium compound, and a hafnium compound is used as a Lewis acid. The present invention relates to a method for producing a polymer (claim 5).

簡易にかつ安価に含フッ素(メタ)アクリル酸エステル系重合体を製造する方法を提供する。   Provided is a method for producing a fluorine-containing (meth) acrylic acid ester polymer easily and inexpensively.

本発明は、(メタ)アクリル酸エステル系重合体に、下記一般式1で表されるフッ素原子含有アルコール

Figure 0004450182
(但し、Rfは分子中に少なくとも1個以上のフッ素原子が含有される炭素数1〜15のフルオロアルキル基又はフルオロアルキルエーテル基であり、nは0〜10の整数を表す。)
を反応させることを特徴とする、含フッ素(メタ)アクリル酸エステル系重合体の製造方法である。 The present invention relates to a (meth) acrylic acid ester polymer, a fluorine atom-containing alcohol represented by the following general formula 1
Figure 0004450182
(However, Rf is a C1-C15 fluoroalkyl group or fluoroalkylether group containing at least one fluorine atom in the molecule, and n represents an integer of 0-10.)
Is a method for producing a fluorine-containing (meth) acrylic acid ester polymer.

本発明の(メタ)アクリル酸エステル系重合体は、特に限定がなく、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸シクロヘキシルなど(メタ)アクリル酸エステル系単量体からなる重合体、及びこれらの共重合体が挙げられる。これらの中で、反応性の観点ならびにコストから考えるとメタクリル酸メチルが好ましい。   The (meth) acrylic acid ester polymer of the present invention is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, ( Examples thereof include polymers composed of (meth) acrylate monomers such as t-butyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate, and copolymers thereof. Among these, methyl methacrylate is preferable from the viewpoint of reactivity and cost.

また、(メタ)アクリル酸、スチレンやα−メチルスチレン、無水マレイン酸などの(メタ)アクリル酸エステル系モノマーと共重合可能な単量体が共重合されていても構わない。   Moreover, the monomer which can be copolymerized with (meth) acrylic acid ester type monomers, such as (meth) acrylic acid, styrene, (alpha) -methylstyrene, and maleic anhydride, may be copolymerized.

本発明の下記一般式1で表されるフッ素原子含有アルコール

Figure 0004450182
におけるRfは1個以上のフッ素原子が含有される炭素数1〜15のフルオロアルキル基又はフルオロエーテル基であれば特に制限はない。 Fluorine atom-containing alcohol represented by the following general formula 1 of the present invention
Figure 0004450182
R f in is not particularly limited as long as it is a fluoroalkyl group having 1 to 15 carbon atoms or a fluoroether group containing one or more fluorine atoms.

ここで言うフルオロアルキル基とは、例えばCF3(CF2b(bは0〜14の整数)やCF2H(CHF)c(CF2d(c,dはそれぞれ0以上の整数で、c+d=0〜14)で表される直鎖構造のものでも、(CF33Cのような分岐構造のものであってもよい。 The fluoroalkyl group mentioned here is, for example, CF 3 (CF 2 ) b (b is an integer of 0 to 14) or CF 2 H (CHF) c (CF 2 ) d (c and d are each an integer of 0 or more. , C + d = 0 to 14) or a branched structure such as (CF 3 ) 3 C.

また、ここで言うフルオロアルキルエーテル基とは、例えばCF3O(CF2eO(CF2f(e+f=1〜14の整数で、eは1以上の整数)やCF2HO(CHF)gO(CF2h(g+h=1〜14の整数で、gは1以上の整数)のように表される直鎖構造のものでも、(CF33CO(CF2j(jは0〜10の整数)のように表される分岐構造のものであってもよい。 The fluoroalkyl ether group referred to here is, for example, CF 3 O (CF 2 ) e O (CF 2 ) f (e + f = 1 to 14, an integer of 1 or more) or CF 2 HO (CHF ) G O (CF 2 ) h (g + h = 1 to 14, where g is an integer of 1 or more) having a linear structure represented by (CF 3 ) 3 CO (CF 2 ) j ( j may be of a branched structure represented as follows:

また、下記一般式1で表されるフッ素原子含有アルコール

Figure 0004450182
の繰返し単位数を表すnについては0〜10の整数であればよいが、フッ素原子による電子吸引性が非常に高い場合は、含フッ素原子アルコールの求核性が低下するため、nは2以上であることがより好ましい。 In addition, a fluorine atom-containing alcohol represented by the following general formula 1
Figure 0004450182
N representing the number of repeating units may be an integer of 0 to 10, but when the electron withdrawing property by the fluorine atom is very high, the nucleophilicity of the fluorine-containing atom alcohol is lowered, so n is 2 or more. It is more preferable that

フッ素原子含有アルコールとしては例えば、2,2,2−トリフルオロ−1−エタノール、2,2,3,3,3−ペンタフルオロ−1−プロパノール、7,7,8,8,8−ペンタフルオロ−1−オクタノール、2,2,3,3,4,4,4−ヘプタフルオロ−1−ブタノール、3,3,4,4,5,5,6,6,6−ノナフルオロ−1−ヘキサノール、4,4,5,5,6,6,7,7,7−ノナフルオロ−1−ヘプタノール、7,7,8,8,9,9,10,10,10−デカノール、2−パーフルオロプロポキシ−2,2,3,3−テトラフルオロプロパノール、2−(パーフルオロヘキシル)エタノール、2−(パーフルオロヘキシル)プロパノール、6−(パーフルオロヘキシル)ヘキサノール、2−(パーフルオロオクチル)エタノール、3−(パーフルオロオクチル)プロパノール、6−(パーフルオロオクチル)ヘキサノール、2−(パーフルオロデシル)エタノール、1H,1H−2,5−ジ(トリフルオロメチル)−3,6−ジオキサウンデカフルオロノナノール、6−(パーフルオロ−1−メチルエチル)−ヘキサノール、2−(パーフルオロ−3−メチルブチル)−エタノール、2−(パーフルオロ−5−メチルヘキシル)−エタノール、2−(パーフルオロ−7−メチルオクチル)−エタノール、1H,1H,3H−テトラフルオロプロパノール、1H,1H,5H−オクタフルオロペンタノール、1H,1H,7H−ドデカフルオロヘプタノール、1H,1H,9H−ヘキサデカフルオロノナノール、2H−ヘキサフルオロ−2−プロパノール、1H,1H,3H−ヘキサフルオロブタノール、2,2−ビス(トリフルオロメチル)プロパノール等を例示できる。   Examples of the fluorine atom-containing alcohol include 2,2,2-trifluoro-1-ethanol, 2,2,3,3,3-pentafluoro-1-propanol, and 7,7,8,8,8-pentafluoro. -1-octanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol, 4,4,5,5,6,6,7,7,7-nonafluoro-1-heptanol, 7,7,8,8,9,9,10,10,10-decanol, 2-perfluoropropoxy- 2,2,3,3-tetrafluoropropanol, 2- (perfluorohexyl) ethanol, 2- (perfluorohexyl) propanol, 6- (perfluorohexyl) hexanol, 2- (perfluorooctyl) ethane Nord, 3- (perfluorooctyl) propanol, 6- (perfluorooctyl) hexanol, 2- (perfluorodecyl) ethanol, 1H, 1H-2,5-di (trifluoromethyl) -3,6-dioxa Undecafluorononanol, 6- (perfluoro-1-methylethyl) -hexanol, 2- (perfluoro-3-methylbutyl) -ethanol, 2- (perfluoro-5-methylhexyl) -ethanol, 2- ( Perfluoro-7-methyloctyl) -ethanol, 1H, 1H, 3H-tetrafluoropropanol, 1H, 1H, 5H-octafluoropentanol, 1H, 1H, 7H-dodecafluoroheptanol, 1H, 1H, 9H-hexa Decafluorononanol, 2H-hexafluoro-2-propanol, 1H, H, 3H-hexafluoro-butanol, 2,2-bis (trifluoromethyl) propanol can be exemplified.

本発明においてはエステル交換触媒存在下で、(メタ)アクリル酸エステル系重合体とフッ素原子含有アルコールと反応させても構わない。エステル交換触媒とは、本発明の反応のように、エステル基の置換基を変換させるエステル交換反応の反応速度を促進するものである。   In the present invention, a (meth) acrylic acid ester polymer and a fluorine atom-containing alcohol may be reacted in the presence of a transesterification catalyst. The transesterification catalyst accelerates the reaction rate of the transesterification reaction for converting the substituent of the ester group as in the reaction of the present invention.

本発明では、一般的に使用されているエステル交換触媒がいずれも使用可能であり、例えばアルカリ金属炭酸塩やアルカリ金属重炭酸塩、アルカリ土類金属炭酸塩、アルカリ土類金属重炭酸塩、アルカリ金属水酸化物、アルカリ土類金属水酸化物、ルイス酸、プロトン酸などを例示できる。   In the present invention, any commonly used transesterification catalyst can be used. For example, alkali metal carbonate, alkali metal bicarbonate, alkaline earth metal carbonate, alkaline earth metal bicarbonate, alkali Examples thereof include metal hydroxides, alkaline earth metal hydroxides, Lewis acids, and protonic acids.

ここでアルカリ金属炭酸塩とは炭酸リチウム、炭酸カリウム、炭酸ナトリウム、炭酸ルビジウム、炭酸セシウム、炭酸フランシウムのことを指し、特に炭酸カリウムと炭酸セシウムが好ましい。   Here, the alkali metal carbonate refers to lithium carbonate, potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, and francium carbonate, and potassium carbonate and cesium carbonate are particularly preferable.

また、アルカリ土類金属炭酸塩とは炭酸マグネシウム、炭酸カルシウム、炭酸ストロンチウム、炭酸バリウムのことを指し、特に炭酸マグネシウムと炭酸カルシウムが好ましい。   The alkaline earth metal carbonate means magnesium carbonate, calcium carbonate, strontium carbonate, or barium carbonate, and magnesium carbonate and calcium carbonate are particularly preferable.

また、アルカリ金属重炭酸塩とは重炭酸リチウム、重炭酸カリウム、重炭酸ナトリウム、重炭酸ルビジウム、重炭酸セシウム、重炭酸フランシウムのことを指し、特に重炭酸カリウムが好ましい。   Alkali metal bicarbonate refers to lithium bicarbonate, potassium bicarbonate, sodium bicarbonate, rubidium bicarbonate, cesium bicarbonate, francium bicarbonate, and potassium bicarbonate is particularly preferred.

また、ルイス酸とは電子対を受容できる化合物であり、具体的にはスズ系化合物、亜鉛系化合物、イッテルビウム系化合物、チタン系化合物、バナジウム系化合物、ジルコニウム系化合物、ハフニウム系化合物等の電子対受容可能な金属化合物があるが、チタン系化合物、バナジウム系化合物、ジルコニウム系化合物、ハフニウム系化合物が好ましい。   A Lewis acid is a compound that can accept an electron pair. Specifically, an electron pair such as a tin compound, a zinc compound, an ytterbium compound, a titanium compound, a vanadium compound, a zirconium compound, or a hafnium compound. Although there are acceptable metal compounds, titanium compounds, vanadium compounds, zirconium compounds, and hafnium compounds are preferred.

チタン系化合物であれば四塩化チタン、三塩化チタン、チタンテトラメトキシド、チタンテトライソプロポキシド、チタンn−テトラブトキシド、チタンジクロロジイソプロポキシドがより好ましい。   Titanium tetrachloride, titanium trichloride, titanium tetramethoxide, titanium tetraisopropoxide, titanium n-tetrabutoxide, and titanium dichlorodiisopropoxide are more preferable for titanium compounds.

バナジウム系化合物であれば4価のバナジウム系化合物がより好ましく、その中でもバナジルクロライド(VOCl2)、バナジルアセチルアセトナート(VO(acac)2)、バナジルトリフレート(一般式VO(SO3CF32)が特に好ましい。 A tetravalent vanadium compound is more preferable if it is a vanadium compound. Among them, vanadyl chloride (VOCl 2 ), vanadyl acetylacetonate (VO (acac) 2 ), vanadyl triflate (general formula VO (SO 3 CF 3 )) 2 ) is particularly preferred.

ジルコニウム系化合物であれば塩化ジルコニウム、アセチルアセトナートジルコニウム、ジルコニウムn−ブトキシド、ジルコニウムt−ブトキシド、ジルコニウムn−プロポキシド、ジルコニウムイソプロポキシド、ジルコニウムエトキシド、炭酸ジルコニウムが好ましい。   Zirconium chloride, acetylacetonate zirconium, zirconium n-butoxide, zirconium t-butoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide and zirconium carbonate are preferred as the zirconium-based compounds.

ハフニウム化合物であれば塩化ハフニウム、ハフニウムテトラt−ブトキシド、アセチルアセトナートハフニウムが好ましい。   In the case of a hafnium compound, hafnium chloride, hafnium tetra-butoxide, and acetylacetonate hafnium are preferable.

また、プロトン酸とは、H+を放出可能な物質であり、具体的には塩化水素、硫化水素、硫酸、酢酸、p−トルエンスルホン酸などを例示できる。 Protonic acid is a substance capable of releasing H + , and specifically includes hydrogen chloride, hydrogen sulfide, sulfuric acid, acetic acid, p-toluenesulfonic acid, and the like.

また、用いるエステル交換触媒は単独で使用しても、複数種を混合して使用しても、エステル交換反応が進行する限り、どちらでも構わない。   Moreover, the transesterification catalyst to be used may be used singly or as a mixture of plural kinds as long as the transesterification proceeds.

本発明におけるフッ素原子含有アルコールの添加量は実質的にエステル交換反応が進行する限りどのような範囲でも可能であるが、(メタ)アクリル酸エステル系重合体中におけるエステル基のモル数(A)に対するフッ素原子含有アルコールのモル数(B)の比{(B)/(A)}とした場合、通常0.01〜2.0の範囲が好ましく、0.02〜1.5の範囲がより好ましい。   The addition amount of the fluorine atom-containing alcohol in the present invention can be any range as long as the transesterification proceeds substantially, but the number of moles of ester groups in the (meth) acrylate polymer (A) When the ratio (B) / (A)} of the number of moles of fluorine atom-containing alcohol to alcohol ((B) / (A)}) is usually preferably in the range of 0.01 to 2.0, more preferably in the range of 0.02 to 1.5. preferable.

本発明におけるエステル交換触媒の添加量は実質的にエステル交換反応が進行する限りどのような範囲でも可能であるが、(メタ)アクリル酸エステル系重合体中におけるエステル基のモル数(A)に対するエステル交換触媒のモル数(C)の比{(C)/(A)}とした場合、通常0.0001〜1.0の範囲が好ましく、0.001〜0.5の範囲がより好ましい。   The addition amount of the transesterification catalyst in the present invention can be in any range as long as the transesterification reaction proceeds substantially, but is based on the number of moles of ester groups (A) in the (meth) acrylic acid ester polymer. When the ratio (C) / (A)} of the number of moles (C) of the transesterification catalyst is used, the range of 0.0001 to 1.0 is usually preferable, and the range of 0.001 to 0.5 is more preferable.

本発明の製造方法においては、(メタ)アクリル酸エステル系重合体をエステル交換反応に対して不活性な非反応性溶媒中に溶解させた後、フッ素原子含有アルコールと反応させることができる。   In the production method of the present invention, the (meth) acrylic acid ester-based polymer can be reacted with a fluorine atom-containing alcohol after being dissolved in a non-reactive solvent inert to the transesterification reaction.

(メタ)アクリル酸エステル系重合体を非反応性溶媒中に溶解させて後、エステル交換反応を行う場合においては、溶解した溶液を加熱、攪拌でき、フッ素原子含有アルコールを添加できる構造であれば特に制限はなく、圧力容器内で行っても、常圧下でガラス容器等を用いて反応を行ってもよい。また、反応副生成物のアルコールを取り除くことにより反応の進行が促進される場合が多く、場合によっては反応副生成物を系外に除外する器具や装置を用いても構わないし、副生成物のみ吸収するようなモレキュラーシーブ等の吸収剤や副生成物のみと反応するような反応剤を使用して反応系から除外しても構わない。   When the (meth) acrylic acid ester polymer is dissolved in a non-reactive solvent and then transesterified, the dissolved solution can be heated and stirred, and the structure can add a fluorine atom-containing alcohol. There is no restriction | limiting in particular, Even if it carries out in a pressure vessel, you may react using a glass container etc. under a normal pressure. In addition, the reaction progress is often promoted by removing the reaction by-product alcohol, and in some cases, it may be possible to use a device or apparatus that excludes the reaction by-product from the system. Absorbents such as molecular sieves that absorb or reactants that react only with by-products may be used and excluded from the reaction system.

用いる非反応性溶媒又はフッ素原子含有アルコールの沸点が非常に低い場合、エステル交換反応は高温での反応が必要な場合が多いため、圧力容器内で行うことが好ましい。   When the boiling point of the non-reactive solvent or the fluorine atom-containing alcohol to be used is very low, the transesterification reaction often requires a reaction at a high temperature.

また、非反応性溶媒としては(メタ)アクリル酸エステル系重合体を溶解させるものであれば特に限定はされないが、反応生成物である含フッ素(メタ)アクリル酸エステル系重合体も溶解できる溶媒が好ましく、ベンゼン、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン、ベンゾトリフルオライド、2−クロロ−ベンゾトリフルオライド等がコスト面からより好ましい。   The non-reactive solvent is not particularly limited as long as it dissolves the (meth) acrylate polymer, but the solvent can also dissolve the fluorine-containing (meth) acrylate polymer that is a reaction product. Benzene, toluene, xylene, chlorobenzene, dichlorobenzene, benzotrifluoride, 2-chloro-benzotrifluoride and the like are more preferable from the viewpoint of cost.

(メタ)アクリル酸エステル系重合体の非反応性溶媒に対する濃度は高い方が製造コストの面からは好ましく、固形分濃度として5〜80%、特に10〜70%が好ましい。   A higher concentration of the (meth) acrylic acid ester polymer with respect to the non-reactive solvent is preferable from the viewpoint of production cost, and a solid content concentration of 5 to 80%, particularly 10 to 70% is preferable.

本発明におけるエステル交換触媒、未反応の含フッ素アルコール及び反応副生成物のアルコールは、常法に従って反応生成物の含フッ素(メタ)アクリル酸エステル系重合体から分離され、必要に応じて濾過、溶剤による抽出、脱揮等の精製処理をして所望の製品として取得される。   The transesterification catalyst, unreacted fluorinated alcohol and reaction by-product alcohol in the present invention are separated from the fluorinated (meth) acrylic acid ester polymer of the reaction product according to a conventional method, and filtered if necessary. It is obtained as a desired product after purification by extraction with a solvent, devolatilization, or the like.

以上のように、(メタ)アクリル酸エステル系重合体をエステル交換触媒存在下に含フッ素アルコールと反応させることにより、その耐溶剤性と撥水性、撥油性、耐熱性を改善することが期待される。   As described above, it is expected to improve the solvent resistance, water repellency, oil repellency and heat resistance by reacting a (meth) acrylic acid ester polymer with a fluorinated alcohol in the presence of a transesterification catalyst. The

[実施例]
本発明を実施例に基づき更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、以下の実施例および比較例で測定した物性の各測定方法は次の通りである。
[Example]
The present invention will be described in more detail based on examples, but the present invention is not limited to only these examples. In addition, each measuring method of the physical property measured in the following Examples and Comparative Examples is as follows.

(1)反応率の測定
反応生成物を1H−NMR(Varian Gemini−300MHz)により、3.5〜3.7ppm付近に検出されるポリメチルメタクリレートのOCH3基の積分値を3で割った値を(D)、4.1〜4.4ppm付近に検出される反応生成物である含フッ素(メタ)アクリル酸エステル系重合体のエステル基のC(=O)OCH2−の積分値を2で割った値を(E)とし、反応率は(E)/{(D)+(E)}として算出した。
(1) Measurement of reaction rate The reaction product was divided by 3 by the integral value of OCH 3 group of polymethyl methacrylate detected in the vicinity of 3.5 to 3.7 ppm by 1 H-NMR (Varian Gemini-300 MHz). The integrated value of C (= O) OCH 2 -of the ester group of the fluorine-containing (meth) acrylic acid ester polymer, which is a reaction product detected in the vicinity of (D), 4.1 to 4.4 ppm. The value divided by 2 was defined as (E), and the reaction rate was calculated as (E) / {(D) + (E)}.

(2)フッ素含有率の測定
反応生成物中のフッ素含有量は、酸素フラスコ燃焼法により反応生成物を分解した後、イオンクロマトグラフ(ダイオネクス製DX−500)、カラムとしてIonPac AG12AとAS12A(4mmφ×250mm)、溶離液として0.3mMのNaHCO3+2.7mMのNa2CO3、溶離液流量を1.2mL/min、電気伝導度検出器にて検出し、フッ素イオン標準液(関東化学製)により作成した検量線から計算した。
(2) Measurement of fluorine content The fluorine content in the reaction product was determined by decomposing the reaction product by an oxygen flask combustion method, and then using an ion chromatograph (DX-500 manufactured by Dionex) and IonPac AG12A and AS12A (4 mmφ) as a column. × 250 mm), 0.3 mM NaHCO 3 +2.7 mM Na 2 CO 3 as an eluent, eluent flow rate 1.2 mL / min, detected with an electric conductivity detector, fluorine ion standard solution (manufactured by Kanto Chemical) ).

(3)ガラス転移温度(Tg)
生成物10mgを用いて、示差走査熱量計(DSC、(株)島津製作所製DSC−50型)を用いて、窒素雰囲気下、昇温速度20℃/minで測定し、中点法により決定した。
(3) Glass transition temperature (Tg)
Using 10 mg of the product, a differential scanning calorimeter (DSC, model DSC-50 manufactured by Shimadzu Corporation) was used to measure under a nitrogen atmosphere at a heating rate of 20 ° C./min, and determined by the midpoint method. .

耐圧10MPaの50mLのオートクレーブ(耐圧硝子工業製)に、市販のポリメチルメタクリレート(住友化学製スミペックスLG)1.0g、フッ素原子含有アルコールである3,3,4,4,5,5,6,6,6−ノナフルオロ−1−ヘキサノールを2.64g、非反応性溶剤としてクロロベンゼンを10ml、エステル交換触媒としてバナジル(IV)トリフレート(VO(SO3CF32)を365mg入れ、反応温度220℃、反応時間9時間にて反応させた。放冷後、反応混合物を塩化メチレンにて4倍に希釈した溶液をメタノールに滴下して再沈澱させ、濾過/乾燥して生成物を回収した。得られた含フッ素(メタ)アクリル酸エステル系重合体の反応率は20%と算出され、フッ素含有率は23wt%、ガラス転位温度は79℃であった。参考として、生成物の1H−NMRスペクトルを図1に示した。 In a 50 mL autoclave (pressure-resistant glass industry) with a pressure resistance of 10 MPa, 1.0 g of commercially available polymethyl methacrylate (Sumipex LG manufactured by Sumitomo Chemical), 3,3,4,4,5,5,6, which is a fluorine atom-containing alcohol 2.64 g of 6,6-nonafluoro-1-hexanol, 10 ml of chlorobenzene as a non-reactive solvent, 365 mg of vanadyl (IV) triflate (VO (SO 3 CF 3 ) 2 ) as a transesterification catalyst were added, and the reaction temperature was 220. The reaction was carried out at 0 ° C. for 9 hours. After allowing to cool, a solution obtained by diluting the reaction mixture 4 times with methylene chloride was added dropwise to methanol for reprecipitation, followed by filtration / drying to recover the product. The reaction rate of the obtained fluorine-containing (meth) acrylate polymer was calculated to be 20%, the fluorine content was 23 wt%, and the glass transition temperature was 79 ° C. For reference, the 1 H-NMR spectrum of the product is shown in FIG.

耐圧10MPaの50mLのオートクレーブ(耐圧硝子工業製)に、市販のポリメチルメタクリレート(住友化学製スミペックスLG)1.0g、フッ素原子含有アルコールである3,3,4,4,5,5,6,6,6−ノナフルオロ−1−ヘキサノールを2.64g、非反応性溶剤として2−クロロ−ベンゾトリフルオライドを10ml、エステル交換触媒として四塩化チタンを100mg入れ、反応温度220℃、反応時間9時間にて反応させた。放冷後、反応混合物を塩化メチレンにて4倍に希釈した溶液をメタノールに滴下して再沈澱させ、濾過/乾燥して生成物を回収した。得られた含フッ素(メタ)アクリル酸エステル系重合体の反応率は30%と算出され、フッ素含有率は30wt%、ガラス転位温度は58℃であった。   In a 50 mL autoclave (pressure-resistant glass industry) with a pressure resistance of 10 MPa, 1.0 g of commercially available polymethyl methacrylate (Sumipex LG manufactured by Sumitomo Chemical), 3,3,4,4,5,5,6, which is a fluorine atom-containing alcohol 2.64 g of 6,6-nonafluoro-1-hexanol, 10 ml of 2-chloro-benzotrifluoride as a non-reactive solvent, and 100 mg of titanium tetrachloride as a transesterification catalyst were added at a reaction temperature of 220 ° C. and a reaction time of 9 hours. And reacted. After allowing to cool, a solution obtained by diluting the reaction mixture 4 times with methylene chloride was added dropwise to methanol for reprecipitation, followed by filtration / drying to recover the product. The reaction rate of the obtained fluorine-containing (meth) acrylic acid ester polymer was calculated to be 30%, the fluorine content was 30 wt%, and the glass transition temperature was 58 ° C.

耐圧10MPaの50mLのオートクレーブ(耐圧硝子工業製)に、市販のポリメチルメタクリレート(住友化学製スミペックスLG)1.0g、フッ素原子含有アルコールである3,3,4,4,5,5,6,6,6−ノナフルオロ−1−ヘキサノールを2.90g、非反応性溶剤として2−クロロ−ベンゾトリフルオライドを10ml、エステル交換触媒として炭酸カリウムを140mg入れ、反応温度220℃、反応時間9時間にて反応させた。放冷後、反応混合物を塩化メチレンにて4倍に希釈した溶液をメタノールに滴下して再沈澱させ、濾過/乾燥して生成物を回収した。得られた含フッ素(メタ)アクリル酸エステル系重合体の反応率は5%と算出され、フッ素含有率は8wt%、ガラス転位温度は98℃であった。   In a 50 mL autoclave (pressure-resistant glass industry) with a pressure resistance of 10 MPa, 1.0 g of commercially available polymethyl methacrylate (Sumipex LG manufactured by Sumitomo Chemical), 3,3,4,4,5,5,6, which is a fluorine atom-containing alcohol 6.90 g of 6,6-nonafluoro-1-hexanol, 10 ml of 2-chloro-benzotrifluoride as a non-reactive solvent, 140 mg of potassium carbonate as a transesterification catalyst, reaction temperature 220 ° C., reaction time 9 hours Reacted. After allowing to cool, a solution obtained by diluting the reaction mixture 4 times with methylene chloride was added dropwise to methanol for reprecipitation, followed by filtration / drying to recover the product. The reaction rate of the obtained fluorine-containing (meth) acrylic acid ester polymer was calculated to be 5%, the fluorine content was 8 wt%, and the glass transition temperature was 98 ° C.

生成物の1H−NMRスペクトル図。 1 H-NMR spectrum diagram of the product.

Claims (5)

(メタ)アクリル酸エステル系重合体に、下記一般式1で表されるフッ素原子含有アルコール
Figure 0004450182
(但し、Rfは少なくとも1個以上のフッ素原子を含有する炭素数1〜15のフルオロアルキル基又はフルオロアルキルエーテル基であり、nは0〜10の整数を表す。)
を反応させることを特徴とする、含フッ素(メタ)アクリル酸エステル系重合体の製造方法。
Fluorine atom-containing alcohol represented by the following general formula 1 to (meth) acrylic acid ester polymer
Figure 0004450182
(However, Rf is a C1-C15 fluoroalkyl group or fluoroalkyl ether group containing at least one fluorine atom, and n represents an integer of 0-10.)
A process for producing a fluorine-containing (meth) acrylic acid ester polymer, characterized in that
エステル交換触媒存在下で反応させることを特徴とする請求項1に記載の含フッ素(メタ)アクリル酸エステル系重合体の製造方法。   The method for producing a fluorine-containing (meth) acrylate polymer according to claim 1, wherein the reaction is carried out in the presence of a transesterification catalyst. エステル交換触媒としてアルカリ金属炭酸塩、アルカリ土類金属炭酸塩、アルカリ金属重炭酸塩、アルカリ金属水酸化物から選ばれる少なくとも1種からなるエステル交換触媒を用いることを特徴とする請求項2に記載の含フッ素(メタ)アクリル酸エステル系重合体の製造方法。   3. The transesterification catalyst comprising at least one selected from alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides is used as the transesterification catalyst. Of producing a fluorine-containing (meth) acrylic acid ester polymer. エステル交換触媒としてルイス酸、プロトン酸から選ばれる少なくとも1種からなるエステル交換触媒を用いることを特徴とする請求項2に記載の含フッ素(メタ)アクリル酸エステル系重合体の製造方法。   The method for producing a fluorine-containing (meth) acrylic acid ester polymer according to claim 2, wherein the transesterification catalyst is at least one transesterification catalyst selected from a Lewis acid and a protonic acid. ルイス酸としてバナジウム系化合物、チタン系化合物、ジルコニウム系化合物、ハフニウム系化合物から選ばれる少なくとも1種からなるエステル交換触媒を用いることを特徴とする請求項4に記載の含フッ素(メタ)アクリル酸エステル系重合体の製造方法。
The fluorine-containing (meth) acrylic acid ester according to claim 4, wherein a transesterification catalyst comprising at least one selected from vanadium compounds, titanium compounds, zirconium compounds, and hafnium compounds is used as a Lewis acid. A method for producing a polymer.
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