JP6998708B2 - Fowling inhibitor - Google Patents
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- JP6998708B2 JP6998708B2 JP2017169934A JP2017169934A JP6998708B2 JP 6998708 B2 JP6998708 B2 JP 6998708B2 JP 2017169934 A JP2017169934 A JP 2017169934A JP 2017169934 A JP2017169934 A JP 2017169934A JP 6998708 B2 JP6998708 B2 JP 6998708B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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Description
本発明は、ファウリング抑制能付与剤に関する。より詳しくは、水処理膜との良好な親和性を有する、ファウリング抑制能付与剤に関する。 The present invention relates to an agent for imparting fouling inhibitory ability. More specifically, the present invention relates to a fouling inhibitory ability-imparting agent having a good affinity with a water treatment membrane.
水処理膜は、不純物を含む水を処理するために用いられる膜であり、世界各国で排水基準、水質基準が強化されるに伴い、使用が広がっている。水処理膜が使用される用途には、浄水処理、プロセス水製造、下水処理、工業排水処理、海水の淡水化等があり、精密ろ過膜、限外ろ過膜、ナノろ過膜、逆浸透膜、イオン交換膜等、種々の水処理膜が用途に応じて使い分けられており、なかでも、逆浸透膜（ＲＯ膜）は、その特性を生かして、脱塩や濃縮などの目的で各種水処理分野において広く用いられている。 Water treatment membranes are membranes used to treat water containing impurities, and their use is expanding as wastewater standards and water quality standards are strengthened around the world. Applications where water treatment membranes are used include microfiltration membranes, process water production, sewage treatment, industrial wastewater treatment, seawater desalination, etc., microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, reverse osmosis membranes, etc. Various water treatment membranes such as ion exchange membranes are used properly according to the application. Among them, reverse osmosis membranes (RO membranes) are used in various water treatment fields for the purpose of desalting and concentration by taking advantage of their characteristics. Widely used in.
従来、使用に伴って生じるＲＯ膜の汚染（ファウリング）により、透過水量（フラックス）が低下することを抑制するために、各種親水性樹脂をＲＯ膜に接触させることで、親水化処理を施すことが開示されている。 Conventionally, in order to suppress a decrease in the amount of permeated water (flux) due to contamination (fouling) of the RO membrane caused by use, various hydrophilic resins are brought into contact with the RO membrane to perform a hydrophilic treatment. Is disclosed.
例えば特許文献１には、下記で表される単量体、及びカチオン性（メタ）アクリル酸エステルを含む単量体組成物を重合して得た共重合体と、水とを含むポリアミド逆浸透膜用の表面処理剤が開示されている。 For example, Patent Document 1 describes a polyamide reverse osmosis containing water and a copolymer obtained by polymerizing a monomer composition represented by the following and a monomer composition containing a cationic (meth) acrylic acid ester. Surface treatment agents for membranes are disclosed.
式中、Ｒ１は水素原子又はメチル基を示し、Ｒ２及びＲ３はそれぞれ独立に炭素数１～４のアルキレン基を示し、Ｒ４、Ｒ５及びＲ６はそれぞれ独立に炭素数１～４のアルキル基を示す。上記表面処理剤は、上記式で表される単量体とカチオン性（メタ）アクリル酸エステルを含む単量体組成物を重合して得た共重合体及び水とを含み、実質的に有機溶剤を含まないので、有機溶剤を除去する設備を必要とせず、環境にも安全であり、ポリアミド逆浸透膜のファウリングを長期にわたり効果的に抑制することができることが開示されている。 In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each independently represent an alkylene group having 1 to 4 carbon atoms, and R 4 , R 5 and R 6 independently represent 1 to 4 carbon atoms. The alkyl group of 4 is shown. The surface treatment agent contains a copolymer obtained by polymerizing a monomer represented by the above formula and a monomer composition containing a cationic (meth) acrylic acid ester, and water, and is substantially organic. It is disclosed that since it does not contain a solvent, it does not require equipment for removing organic solvents, is environmentally safe, and can effectively suppress fouling of a polyamide reverse osmosis membrane for a long period of time.
例えば引用文献２には、逆浸透膜に、ポリアルキレンオキサイド鎖を有する変性ポリビニルアルコールを接触させることを特徴とする逆浸透膜の親水化処理方法が開示されている。上記方法によれば、ＲＯ膜を、ポリアルキレンオキサイド鎖を有する変性ポリビニルアルコールで処理することにより、親水性を付与すると共に、その親水化効果を長期に亘って維持できること、ポリアルキレンオキサイド鎖を有する変性ポリビニルアルコールであれば、親水化処理によるＲＯ膜のフラックスの低下を抑制することができる上に、従来のＰＶＡと比較して、その水溶液の調製が容易であることが開示されている。 For example, Cited Document 2 discloses a method for hydrophilizing a reverse osmosis membrane, which comprises contacting a modified polyvinyl alcohol having a polyalkylene oxide chain with the reverse osmosis membrane. According to the above method, the RO film is treated with a modified polyvinyl alcohol having a polyalkylene oxide chain to impart hydrophilicity, and the hydrophilic effect can be maintained for a long period of time, and the RO film has a polyalkylene oxide chain. It is disclosed that the modified polyvinyl alcohol can suppress a decrease in the flux of the RO film due to the hydrophilization treatment, and it is easier to prepare an aqueous solution thereof as compared with the conventional PVA.
例えば引用文献３には、逆浸透膜に、ポリアルキレンオキサイド鎖を有するベタイン化合物を接触させることを特徴とする逆浸透膜の耐汚染化処理方法が開示されている。上記方法によれば、ＲＯ膜を、ポリアルキレンオキサイド鎖を有するベタイン化合物で処理することにより、ＲＯ膜の耐汚染性を高め、またその耐汚染化効果を長期に亘って維持することができること、ポリアルキレンオキサイド鎖を有するベタイン化合物であれば、耐汚染化処理によるＲＯ膜の初期フラックスの低下を抑制することもできることが開示されている。 For example, Cited Document 3 discloses a stain-resistant treatment method for a reverse osmosis membrane, which comprises contacting a betaine compound having a polyalkylene oxide chain with the reverse osmosis membrane. According to the above method, by treating the RO membrane with a betaine compound having a polyalkylene oxide chain, the stain resistance of the RO membrane can be enhanced and the stain resistance effect can be maintained for a long period of time. It is disclosed that a betaine compound having a polyalkylene oxide chain can also suppress a decrease in the initial flux of the RO membrane due to the stain resistance treatment.
例えば引用文献４には、下記式の構成単位［Ａ］を１０～８０モル％と、下記式（２）の構成単位［Ｂ］を２０～９０モル％と、を有する重量平均分子量が２０，０００～１５０，０００の共重合体からなる多孔質濾過膜用のファウリング抑制剤が開示されている。 For example, in Cited Document 4, the weight average molecular weight having the structural unit [A] of the following formula of 10 to 80 mol% and the structural unit [B] of the following formula (2) of 20 to 90 mol% is 20, Disclosed are fouling inhibitors for porous filtration membranes consisting of 000 to 150,000 copolymers.
［式（１）中、Ｒ１は水素またはメチル基、Ｒ２はアルキル基、ｎは２～２５の整数である。］
上記のファウリング抑制剤は、上記特定構造及び分子量を有する共重合体からなり、多孔質濾過膜に付着させることにより、水処理時のファウリングを効果的に抑制すること、ファウリング発生時のアルカリ等の薬品洗浄に対する耐性が高く、薬品洗浄時に多孔質濾過膜から脱離し難いので、薬品洗浄後も十分なファウリング抑制効果を発揮すること、が開示されている。
[In formula (1), R 1 is a hydrogen or methyl group, R 2 is an alkyl group, and n is an integer of 2 to 25. ]
The above-mentioned fouling inhibitor is composed of a polymer having the above-mentioned specific structure and molecular weight, and by adhering to a porous filtration membrane, it effectively suppresses fouling during water treatment, and when fouling occurs. It is disclosed that since it has high resistance to chemical cleaning such as alkali and is difficult to be separated from the porous filtration membrane during chemical cleaning, it exhibits a sufficient fouling suppressing effect even after chemical cleaning.
上記の通り、ファウリング抑制のための各種親水性樹脂が提案されているが、ＲＯ膜は疎水性であるため、親水性樹脂との親和性（例えば、付着性や相溶性）が十分でなく、例えば、長期の使用において、ＲＯ膜から親水性樹脂が剥離してしまい、ファウリング抑制能が失われてしまう、という課題があった。
よって、本発明は、ＲＯ膜に対する良好な付着性を有し、ファウリング抑制能に優れたファウリング抑制能付与剤を提供することを目的とする。
As described above, various hydrophilic resins for suppressing fouling have been proposed, but since the RO membrane is hydrophobic, the affinity with the hydrophilic resin (for example, adhesion and compatibility) is not sufficient. For example, in long-term use, there is a problem that the hydrophilic resin is peeled off from the RO membrane and the fouling inhibitory ability is lost.
Therefore, an object of the present invention is to provide an agent for imparting fouling inhibitory ability, which has good adhesion to RO membrane and is excellent in fouling inhibitory ability.
本発明者は、上記目的を達成するために種々検討を行い、本発明に想到した。
すなわち、本発明は、下記一般式（１）で表される構造単位〔Ａ〕、および／または、下記一般式（２）で表される構造単位〔Ｂ〕を有する共重合体を含む、ファウリング抑制能付与剤である。
The present inventor has made various studies in order to achieve the above object, and came up with the present invention.
That is, the present invention comprises a copolymer having a structural unit [A] represented by the following general formula (1) and / or a structural unit [B] represented by the following general formula (2). It is a ring-suppressing ability-imparting agent.
（式中、Ｒ１は水素原子またはメチル基を表す。Ｒ２は直接結合、－ＣＨ２－、－ＣＨ２ＣＨ２－、または－ＣＯ－を表す。Ｒ３は同一若しくは異なって炭素数１～２０のアルキレン基を表す。Ｘは－ＣＨ２ＣＨ（ＯＨ）ＣＨ２（ＯＨ）又は－ＣＨ（－ＣＨ２ＯＨ）２を表す。ｎはオキシアルキレン基の付加モル数であって、０～１００の数を表す。） (In the formula, R 1 represents a hydrogen atom or a methyl group. R 2 represents a direct bond, -CH 2-, -CH 2 CH 2- , or -CO-. R 3 has the same or different carbon number 1 Represents an alkylene group of -20. X represents -CH 2 CH (OH) CH 2 (OH) or -CH (-CH 2 OH) 2. n is the number of added moles of the oxyalkylene group, from 0 to. Represents a number of 100.)
（式中、Ｒ１は水素原子またはメチル基を表す。Ｒ２は直接結合、－ＣＨ２－、－ＣＨ２ＣＨ２－、または－ＣＯ－を表す。Ｒ３は同一若しくは異なって炭素数１～２０のアルキレン基を表す。Ｒ４は水素原子または炭素数１～２０のアルキル基を表す。ｎはオキシアルキレン基の付加モル数であって、１～１００の数を表す。） (In the formula, R 1 represents a hydrogen atom or a methyl group. R 2 represents a direct bond, -CH 2-, -CH 2 CH 2- , or -CO-. R 3 has the same or different carbon number 1 Represents an alkylene group of up to 20. R 4 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. N is the number of added moles of an oxyalkylene group and represents a number of 1 to 100.)
本発明によれば、上記共重合体はＲＯ膜への親和性が良好であるため、長期に亘って膜に付着することができる。よって、ファウリング抑制能を長期間維持することが可能である。 According to the present invention, since the above-mentioned copolymer has a good affinity for the RO membrane, it can adhere to the membrane for a long period of time. Therefore, it is possible to maintain the fouling inhibitory ability for a long period of time.
以下に、本発明を詳細に説明する。
なお、以下において記載する本発明の個々の好ましい形態を２つ以上組み合わせたものもまた、本発明の好ましい形態である。
Hereinafter, the present invention will be described in detail.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
＜ＲＯ膜＞
本発明が適用されるＲＯ膜としては、特に制限は無く、例えば酢酸セルロース系、芳香族ポリアミド系、ポリビニルアルコール系、ポリスルホン系等が用いられる。これらの構造としては、中空糸膜、スパイラル膜、チューブラー膜等が例示される。この中でも、芳香族ポリアミドを緻密層とするポリアミド系ＲＯ膜、及びポリアミド系のナノろ過膜、すなわち、ナノろ過膜を含有する広義のＲＯ膜であることが好ましい。なお、芳香族ポリアミド系には、芳香族ポリイミド系を含む。また、新しい膜や使用後の膜、劣化した膜などにも問題なく適用が可能である。
<RO membrane>
The RO membrane to which the present invention is applied is not particularly limited, and for example, cellulose acetate-based, aromatic polyamide-based, polyvinyl alcohol-based, polysulfone-based, and the like are used. Examples of these structures include hollow fiber membranes, spiral membranes, tubular membranes, and the like. Among these, a polyamide-based RO membrane having an aromatic polyamide as a dense layer and a polyamide-based nanofiltration membrane, that is, an RO membrane in a broad sense containing a nanofiltration membrane is preferable. The aromatic polyamide system includes an aromatic polyimide system. In addition, it can be applied to new films, used films, deteriorated films, etc. without any problem.
＜構造単位〔Ａ〕、および／または、構造単位〔Ｂ〕を有する共重合体＞
本発明において、ＲＯ膜のファウリング抑制能付与剤に用いる共重合体（以下、本発明の共重合体）は、上記一般式（１）で表される構造単位〔Ａ〕、および／または、上記一般式（２）で表される構造単位〔Ｂ〕を有する。一般式（１）で表される構造単位〔Ａ〕は下記一般式（３）で表される不飽和単量体を、一般式（２）で表される構造単位〔Ｂ〕は、下記一般式（４）で表される不飽和単量体を重合することにより形成することが好ましい。
<Copolymer having structural unit [A] and / or structural unit [B]>
In the present invention, the copolymer used as the agent for imparting the ability to suppress fouling of the RO film (hereinafter referred to as the copolymer of the present invention) is a structural unit [A] represented by the above general formula (1) and / or. It has a structural unit [B] represented by the above general formula (2). The structural unit [A] represented by the general formula (1) is an unsaturated monomer represented by the following general formula (3), and the structural unit [B] represented by the general formula (2) is the following general. It is preferably formed by polymerizing the unsaturated monomer represented by the formula (4).
（式中、Ｒ１、Ｒ２、Ｒ３、Ｘ、およびｎは、一般式（１）と同様である。） (In the formula, R 1 , R 2 , R 3 , X, and n are the same as those in the general formula (1).)
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、およびｎは、一般式（２）と同様である。）
上記一般式（１）および（３）において；
Ｒ１は水素原子またはメチル基を表すが、膜への親和性の観点から、メチル基であることが好ましい。Ｒ２は直接結合、－ＣＨ２－、－ＣＨ２ＣＨ２－、または－ＣＯ－を表すが、親水性の観点から、－ＣＯ－であることが好ましい。Ｒ３は同一若しくは異なって炭素数１～２０のアルキレン基を表すが、親水性の観点から、２～３であることが好ましい。ｎはオキシアルキレン基の付加モル数であって、好ましくは平均付加モル数であって、０～１００の数を示すが、膜への親和性の観点から、ｎは０以上５以下が好ましい。なお、平均付加モル数を算出する際には、ｎ＝１００以上の単量体を含めてもよい。
(In the formula, R 1 , R 2 , R 3 , R 4 , and n are the same as those in the general formula (2).)
In the above general formulas (1) and (3);
Although R 1 represents a hydrogen atom or a methyl group, it is preferably a methyl group from the viewpoint of affinity for the membrane. R 2 represents direct binding, -CH 2-, -CH 2 CH 2- , or -CO-, but is preferably -CO- from the viewpoint of hydrophilicity. R 3 represents the same or different alkylene group having 1 to 20 carbon atoms, but is preferably 2 to 3 from the viewpoint of hydrophilicity. n is the number of added moles of the oxyalkylene group, preferably the average number of added moles, and indicates a number of 0 to 100, but from the viewpoint of affinity for the membrane, n is preferably 0 or more and 5 or less. When calculating the average number of moles added, a monomer having n = 100 or more may be included.
上記一般式（３）で表される単量体としては、例えば、グリセロール（メタ）アクリレート等が挙げられるが、膜への親和性の点からグリセロールメタクリレートが好ましい。上記一般式（３）で表される単量体は、１種を単独で用いてもよいし、２種以上を併用してもよい。 Examples of the monomer represented by the general formula (3) include glycerol (meth) acrylate, and glycerol methacrylate is preferable from the viewpoint of affinity for the membrane. As the monomer represented by the general formula (3), one type may be used alone, or two or more types may be used in combination.
本発明における共重合体において、上記一般式（１）で表される構造単位〔Ａ〕は、ファウリング抑制効果の観点から、全構造単位１００質量％に対して、４０～９０質量％含有することが好ましい。 In the copolymer of the present invention, the structural unit [A] represented by the above general formula (1) is contained in an amount of 40 to 90% by mass with respect to 100% by mass of the total structural unit from the viewpoint of the fouling suppressing effect. Is preferable.
上記一般式（２）および（４）において；
Ｒ１は水素原子またはメチル基を表すが、親水性の観点から、水素原子であることが好ましい。Ｒ２は直接結合、－ＣＨ２－、－ＣＨ２ＣＨ２－、または－ＣＯ－を表すが、親水性の観点から、－ＣＯ－であることが好ましい。Ｒ３は同一若しくは異なって炭素数１～２０のアルキレン基を表すが、親水性の観点から、２～３であることが好ましい。Ｒ４は水素原子または炭素数１～２０のアルキル基を表すが、親水性の観点から、１～５であることが好ましい。ｎはオキシアルキレン基の付加モル数であって、好ましくは平均付加モル数であって、１～１００の数を示すが、親水性の観点から、ｎは１以上３０以下が好ましい。なお、平均付加モル数を算出する際には、ｎ＝０および１００以上の単量体を含めてもよい。
In the above general formulas (2) and (4);
Although R 1 represents a hydrogen atom or a methyl group, it is preferably a hydrogen atom from the viewpoint of hydrophilicity. R 2 represents direct binding, -CH 2-, -CH 2 CH 2- , or -CO-, but is preferably -CO- from the viewpoint of hydrophilicity. R 3 represents the same or different alkylene group having 1 to 20 carbon atoms, but is preferably 2 to 3 from the viewpoint of hydrophilicity. R 4 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and is preferably 1 to 5 from the viewpoint of hydrophilicity. n is the number of added moles of the oxyalkylene group, preferably the average number of added moles, indicating a number of 1 to 100, but from the viewpoint of hydrophilicity, n is preferably 1 or more and 30 or less. When calculating the average number of moles added, n = 0 and 100 or more monomers may be included.
上記一般式（４）で表される単量体としては、例えば、エトキシ－ジエチレングリコール（メタ）アクリレート、メトキシ－トリエチレングリコール（メタ）アクリレート、２－エチルヘキシル－ジグルコー（メタ）アクリレート、メトキシ－ポリエチレングリコール（メタ）アクリレート、メトキシ－ジプロピレングリコール（メタ）アクリレート、フェノキシ－ジエチレングリコールアクリレート、フェノキシ－ポリエチレングリコール（メタ）アクリレート等のアルコキシアルキレングリコール（メタ）アクリレート）等が挙げられるが、親水性の点からメトキシ－ポリエチレングリコールアクリレートが好ましい。上記一般式（４）で表される単量体は、１種を単独で用いてもよいし、２種以上を併用してもよい。 Examples of the monomer represented by the general formula (4) include ethoxy-diethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, 2-ethylhexyl-digluco (meth) acrylate, and methoxy-polyethylene glycol. Examples thereof include (meth) acrylate, methoxy-dipropylene glycol (meth) acrylate, phenoxy-diethylene glycol acrylate, alkoxyalkylene glycol (meth) acrylate such as phenoxy-polyethylene glycol (meth) acrylate), and methoxy from the viewpoint of hydrophilicity. -Polyethylene glycol acrylate is preferred. As the monomer represented by the general formula (4), one type may be used alone, or two or more types may be used in combination.
本発明における共重合体において、上記一般式（２）で表される構造単位〔Ｂ〕は、ファウリング抑制効果の観点から、全構造単位１００質量％に対して、１０～６０質量％含有することが好ましく、２０～４０質量％含有することがより好ましい。 In the copolymer of the present invention, the structural unit [B] represented by the above general formula (2) is contained in an amount of 10 to 60% by mass with respect to 100% by mass of the total structural unit from the viewpoint of the fouling suppressing effect. It is preferably contained in an amount of 20 to 40% by mass, more preferably 20 to 40% by mass.
また、本発明における共重合体は、一般式（３）および（４）以外の単量体に由来する構造単位を有してもよい。一般式（３）および（４）以外の単量体としては、アミン等のカチオン性基、スルホン酸基、エポキシ基を含む化合物等が挙げられる。 Further, the copolymer in the present invention may have a structural unit derived from a monomer other than the general formulas (3) and (4). Examples of the monomer other than the general formulas (3) and (4) include compounds containing a cationic group such as an amine, a sulfonic acid group, and an epoxy group.
本発明において一般式（３）および（４）以外の単量体に由来する構造単位とは、一般式（３）および（４）以外の単量体に由来する構造単位の炭素－炭素二重結合（Ｃ＝Ｃ）が炭素－炭素単結合（Ｃ－Ｃ）に置き換わった構造であり、典型的には不飽和単量体が重合して形成される構造単位である。ただし、実際に不飽和結合単量体が重合して形成された構造に限らず、不飽和単量体の炭素－炭素二重結合（Ｃ＝Ｃ）が炭素－炭素単結合（Ｃ－Ｃ）に置き換わった構造単位であれば、不飽和単量体に由来する構造単位に該当する。 In the present invention, the structural unit derived from a monomer other than the general formulas (3) and (4) is a carbon-carbon double bond of a structural unit derived from a monomer other than the general formulas (3) and (4). It is a structure in which a bond (C = C) is replaced with a carbon-carbon single bond (CC), and is typically a structural unit formed by polymerizing an unsaturated monomer. However, the structure is not limited to the structure formed by actually polymerizing the unsaturated bond monomer, and the carbon-carbon double bond (C = C) of the unsaturated monomer is a carbon-carbon single bond (CC). If it is a structural unit replaced with, it corresponds to a structural unit derived from an unsaturated monomer.
本発明の共重合体の製造方法は特に限定されない。好ましくは、一般式（３）で表される単量体、一般式（４）で表される単量体、必要に応じて一般式（３）で表される単量体および一般式（４）で表される単量体以外の単量体（以下、「その他の単量体」ともいう）を重合して製造することが好ましい。上記重合は、例えばラジカル重合、カチオン重合、アニオン重合等、通常の共重合反応に従って行うことができる。重合は、ラジカル重合開始剤、カチオン重合性開始剤、アニオン重合性開始剤などの重合開始剤の存在下で行うことが好ましい。重合開始剤の使用量は、単量体１モルに対し、０．００１モル以上１モル以下の割合で使用することがより好ましい。重合は、熱重合や光重合で行うことが好ましい。 The method for producing the copolymer of the present invention is not particularly limited. Preferably, the monomer represented by the general formula (3), the monomer represented by the general formula (4), the monomer represented by the general formula (3) and the general formula (4) are preferable. ) Is preferably polymerized and produced by polymerizing a monomer other than the monomer represented by) (hereinafter, also referred to as “other monomer”). The above polymerization can be carried out according to a usual copolymerization reaction such as radical polymerization, cationic polymerization, anionic polymerization and the like. The polymerization is preferably carried out in the presence of a polymerization initiator such as a radical polymerization initiator, a cationically polymerizable initiator and an anionic polymerizable initiator. The amount of the polymerization initiator used is more preferably 0.001 mol or more and 1 mol or less with respect to 1 mol of the monomer. The polymerization is preferably carried out by thermal polymerization or photopolymerization.
本発明の共重合体は、重量平均分子量が５０００～２０００００であることが好ましい。なお、共重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて、ポリエチレングリコール換算により測定することができる。 The copolymer of the present invention preferably has a weight average molecular weight of 5000 to 200,000. The weight average molecular weight of the copolymer can be measured by gel permeation chromatography (GPC) in terms of polyethylene glycol.
本発明の共重合体は、通常、０．１～５０００ｍｇ／Ｌ、好ましくは１～１０００ｍｇ／Ｌ程度の濃度の水溶液で、ＲＯ膜のファウリング抑止能付与剤として用いられる。この濃度が低すぎると、目的とするファウリング抑止能を得るための処理時間を長く要するため非効率であり、逆にこの濃度が高すぎると、水溶液の粘性が高くなり、ＲＯ膜への接触処理時の取り扱い面で好ましくない。 The copolymer of the present invention is usually an aqueous solution having a concentration of about 0.1 to 5000 mg / L, preferably about 1 to 1000 mg / L, and is used as an agent for imparting fouling inhibitory ability of RO membrane. If this concentration is too low, it takes a long time to obtain the desired fouling deterrent ability, which is inefficient. On the contrary, if this concentration is too high, the viscosity of the aqueous solution becomes high and the contact with the RO membrane is increased. It is not preferable in terms of handling during processing.
本発明の共重合体を有する水溶液の調整に用いる水としては、特に制限はなく、脱塩水などのイオン負荷の低い水が用いられるが、ＲＯ膜への供給水に本発明の共重合体を直接添加して処理することも可能である。 The water used for preparing the aqueous solution having the copolymer of the present invention is not particularly limited, and water having a low ion load such as desalinated water is used, but the copolymer of the present invention is used as the water supplied to the RO membrane. It is also possible to add it directly and treat it.
＜ファウリング抑制能付与剤＞
本発明のファウリング抑制能付与剤は、本発明の共重合体を含む。本発明のファウリング抑制能付与剤は、本発明の目的を阻害しない範囲で、添加剤として、リン酸塩等のｐＨ安定剤、次亜塩素酸ナトリウム等の抗菌成分、メタノール、エタノール、プロパノールなどの低級アルコールを含有してもよいが、本発明はかかる例示に限定されるものではない。これらの添加剤および溶媒は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。本発明のファウリング抑制能付与剤は、本発明の共重合体を０．１質量％以上、１００質量％以下含有することが好ましい。
<Fowling inhibitory agent>
The fouling inhibitory ability-imparting agent of the present invention contains the copolymer of the present invention. The fouling inhibitory ability-imparting agent of the present invention can be used as an additive such as a pH stabilizer such as phosphate, an antibacterial component such as sodium hypochlorite, methanol, ethanol, propanol and the like, as long as the object of the present invention is not impaired. The lower alcohol may be contained, but the present invention is not limited to such an example. These additives and solvents may be used alone or in combination of two or more. The fouling inhibitory ability-imparting agent of the present invention preferably contains the copolymer of the present invention in an amount of 0.1% by mass or more and 100% by mass or less.
＜ＲＯ膜へのファウリング抑制能付与方法＞
本発明のファウリング抑制能付与剤をＲＯ膜へ接触させることで、ＲＯ膜へのファウリング抑制能を付与ことが可能である。本発明のファウリング抑制能付与剤をＲＯ膜へ接触させる方法に関して、特に限定はないが、本発明のファウリング抑制能付与剤の水溶液を、ＲＯ膜に加圧通水して接触させることが好ましい。
<Method of imparting fouling inhibitory ability to RO membrane>
By contacting the fouling inhibitory ability-imparting agent of the present invention with the RO membrane, it is possible to impart the fouling inhibitory ability to the RO membrane. The method for contacting the fouling inhibitory ability-imparting agent of the present invention with the RO membrane is not particularly limited, but the aqueous solution of the fouling inhibitory ability-imparting agent of the present invention may be brought into contact with the RO membrane under pressure. preferable.
すなわち、例えば、液導入口と液排出口を有する容器内を、被処理ＲＯ膜で仕切り、液導入口から本発明のファウリング抑制能付与剤の水溶液を導入して、ＲＯ膜を通過させて、液排出口から排出させる方法が挙げられる。この場合、通常のＲＯ膜分離装置のＲＯ膜モジュールのＲＯ供給水に対して、前述の如く、本発明のファウリング抑制能付与剤を直接添加して、ファウリング抑制能付与を行うこともできる。すなわち、本発明によるファウリング抑制能付与方法は、既存のＲＯ膜分離装置のＲＯ膜モジュールに対して、ＲＯ膜分離処理中に、ＲＯ膜の被処理水に本発明のファウリング抑制能付与剤を添加して実施することもできるし、ＲＯ膜分離処理を中断して実施することもできる。 That is, for example, the inside of the container having the liquid introduction port and the liquid discharge port is partitioned by the RO membrane to be treated, and the aqueous solution of the fouling inhibitory ability-imparting agent of the present invention is introduced from the liquid introduction port and passed through the RO membrane. , A method of discharging from the liquid discharge port can be mentioned. In this case, as described above, the fouling inhibitory ability-imparting agent of the present invention can be directly added to the RO feed water of the RO membrane module of a normal RO membrane separation device to impart the fouling inhibitory ability. .. That is, in the method for imparting the fouling inhibitory ability according to the present invention, the fouling inhibitory ability imparting agent of the present invention is applied to the water to be treated of the RO membrane during the RO membrane separation treatment for the RO membrane module of the existing RO membrane separator. Can be carried out by adding the above, or the RO membrane separation treatment can be interrupted and carried out.
上記ファウリング抑制能付与の処理を、加圧通水する際の圧力に特に制限はないが、０．１～２．０ＭＰａの範囲が好ましい。なお、上記ファウリング抑制能付与の処理時における通水には、通常ＲＯ膜の洗浄で使用するポンプが用いられ、この場合、ポンプの能力から、通水圧力０．１～０．５Ｍｐａの範囲が好ましい。通水する際のフラックスに特に制限はないが、０．１～１．０ｍ／ｄａｙ程度が好ましい。上記通水条件が低すぎると、十分なファウリング抑制能の効果が得られず、高すぎると、フラックス低下が大きくなる懸念がある。 The pressure for imparting the fouling suppressing ability is not particularly limited, but is preferably in the range of 0.1 to 2.0 MPa. A pump normally used for cleaning RO membranes is used for water flow during the treatment for imparting the fouling inhibitory ability. In this case, the water flow pressure is in the range of 0.1 to 0.5 Mpa due to the capacity of the pump. Is preferable. The flux for passing water is not particularly limited, but is preferably about 0.1 to 1.0 m / day. If the water flow condition is too low, the effect of sufficient fouling suppressing ability cannot be obtained, and if it is too high, there is a concern that the flux decrease becomes large.
上記ファウリング抑制能付与の処理時間は特に制限されないが、１時間以上１０００時間以下が好ましく、２時間以上３００時間以下がさらに好ましい。処理時間が短すぎる場合、十分なファウリング抑制能の効果が得られず、処理時間が長すぎる場合、フラックスが低下しすぎる懸念がある。 The processing time for imparting the fouling inhibitory ability is not particularly limited, but is preferably 1 hour or more and 1000 hours or less, and more preferably 2 hours or more and 300 hours or less. If the treatment time is too short, the effect of sufficient fouling suppressing ability cannot be obtained, and if the treatment time is too long, there is a concern that the flux will drop too much.
上記ファウリング抑制能付与の処理温度（水温）は特に制限されないが、１０～３５℃であることが好ましい。水温が低すぎると、フラックスが低下し、接触効率が低下する懸念がある。一方、水温が高すぎると、膜素材の変性等の問題が生じる可能性がある。 The treatment temperature (water temperature) for imparting the fouling suppressing ability is not particularly limited, but is preferably 10 to 35 ° C. If the water temperature is too low, there is a concern that the flux will decrease and the contact efficiency will decrease. On the other hand, if the water temperature is too high, problems such as denaturation of the membrane material may occur.
上記ファウリング抑制能付与の処理を施したＲＯ膜は、超純水製造システム、排水回収システム、その他水処理システムにおいて好適に使用することができる。 The RO membrane subjected to the treatment for imparting the fouling suppressing ability can be suitably used in an ultrapure water production system, a wastewater recovery system, and other water treatment systems.
本発明のファウリング抑制能付与剤は、ＲＯ膜の形成前に、ＲＯ膜の原料に混合（例えば溶媒存在下で混合したり、バルクで混練したり）することや、ＲＯ膜の原料樹脂表面にグラフト重合等により結合させることや、コーティングすることにより、ＲＯ膜にファウリング抑制能を付与しても良い。 The fouling inhibitory ability-imparting agent of the present invention can be mixed with the raw material of the RO film (for example, mixed in the presence of a solvent or kneaded in bulk) before the formation of the RO film, or the surface of the raw material resin of the RO film. The RO membrane may be imparted with the ability to suppress fouling by binding to the RO membrane by graft polymerization or the like or by coating the RO membrane.
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例にのみ限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味するものとする。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".
＜合成例１＞
温度計、還流冷却器、攪拌機を備えた容量２００ｍＬのガラス製セパラブルフラスコに、純水６０ｇを仕込み、攪拌下、８０℃になるまで昇温した。
次いで、攪拌下、重合反応系中に、グリセロールモノメタクリレート（以下、ＧＬＭＭＡと称す）１２．８ｇ、新中村化学社製メトキシポリエチレングリコール＃４００アクリレート（以下、ＡＭ－９０Ｇと称す）２５．７ｇ、２質量％過硫酸ナトリウム水溶液（以下、２％ＮａＰＳと称す）２０ｇ、３５質量％亜硫酸水素ナトリウム水溶液（以下、３５％ＳＢＳと称す）０．７６ｇ、純水２０ｇを、それぞれ別個の滴下ノズルより滴下した。各滴下液の滴下時間は、ＧＬＭＭＡを１８０分間およびＡＭ－９０Ｇを１８０分間、２％ＮａＰＳを２１０分間、３５％ＳＢＳを１８０分間、純水を１８０分間とした。上記各滴下は、すべて同時に滴下を開始し、滴下速度は一定とし、連続的に滴下した。
滴下終了後、更に３０分間に亘って反応溶液を８０℃に保持して熟成し、重合を完結させた。
このようにして、重量平均分子量が４７２００の共重合体（１）を得た。結果を表１に示した。
<Synthesis example 1>
60 g of pure water was placed in a glass separable flask having a capacity of 200 mL equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 80 ° C. under stirring.
Next, under stirring, 12.8 g of glycerol monomethacrylate (hereinafter referred to as GLMMA) and 25.7 g of methoxypolyethylene glycol # 400 acrylate (hereinafter referred to as AM-90G) manufactured by Shin-Nakamura Chemical Co., Ltd. were added to the polymerization reaction system. 20 g of a mass% sodium persulfite aqueous solution (hereinafter referred to as 2% NaPS), 0.76 g of a 35 mass% sodium hydrogen sulfite aqueous solution (hereinafter referred to as 35% SBS), and 20 g of pure water were dropped from separate dropping nozzles. .. The dropping time of each dropping liquid was 180 minutes for GLMMA, 180 minutes for AM-90G, 210 minutes for 2% NaPS, 180 minutes for 35% SBS, and 180 minutes for pure water. All of the above drops were started at the same time, the dropping rate was kept constant, and the drops were continued.
After completion of the dropping, the reaction solution was kept at 80 ° C. for another 30 minutes and aged to complete the polymerization.
In this way, a copolymer (1) having a weight average molecular weight of 47200 was obtained. The results are shown in Table 1.
＜合成例２～８＞
合成例１において、単量体組成比（ｍｏｌ％）を表１に記載の比率とした以外は、合成例１と同様の手順にて、重合体２～８を得た。
<Synthesis Examples 2-8>
Polymers 2 to 8 were obtained in the same procedure as in Synthesis Example 1 except that the monomer composition ratio (mol%) was set to the ratio shown in Table 1.
＜分子量測定＞
合成例１～６で得られた重合体１～６の分子量測定は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて、以下の条件で測定を行った。結果を表１に示す。
装置：東ソー株式会社製 ＨＬＣ－８３２０ＧＰＣ
検出器：ＲＩ
カラム：昭和電工株式会社製 Ｓｈｏｄｅｘ Ａｓａｈｉｐａｋ ＧＦ－３１０－ＨＱ、ＧＦ－７１０－ＨＱ、ＧＦ－１Ｇ ７Ｂ
カラム温度：４０℃
流速：０．５ｍｌ／ｍｉｎ
検量線：創和科学株式会社製 ＰＯＬＥＴＨＹＬＥＮＥ ＧＬＹＣＯＬ ＳＴＡＮＤＡＲＤ
溶離液：０．１Ｍ酢酸ナトリウム水溶液／アセトニトリル＝７５／２５ｗｔ％
<Molecular weight measurement>
The molecular weights of the polymers 1 to 6 obtained in Synthesis Examples 1 to 6 were measured by gel permeation chromatography (GPC) under the following conditions. The results are shown in Table 1.
Equipment: HLC-8320GPC manufactured by Tosoh Corporation
Detector: RI
Column: Showa Denko Corporation Shodex Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B
Column temperature: 40 ° C
Flow velocity: 0.5 ml / min
Calibration curve: POLETHYLENE GLYCOL STANDARD manufactured by Sowa Kagaku Co., Ltd.
Eluent: 0.1 M aqueous sodium acetate solution / acetonitrile = 75/25 wt%
＜実施例１＞
ポリイミド膜（宇部興産社製、ユーピレックス７５μｍ、１５ｍｍ×５０ｍｍ）の試験片（すなわち、浸漬前の試験片）を、合成例１で得られた重合体１の４％水溶液（水溶液温度２５℃）に６０分間浸漬したのち、１３０℃で６０分間乾燥し、これを「浸漬後の試験片」とした。浸漬前後の試験片重量変化から、ポリイミド膜に対する重合体の吸着量（％）を算出した。結果を表１に記載する。なお、フラットシートメンブレンＳＷＣ５（日東電工（株）社製）等の芳香族ポリアミド系ＲＯ膜においても、同様の評価が可能である。
<Example 1>
A test piece of a polyimide film (manufactured by Ube Industries, Ltd., Upirex 75 μm, 15 mm × 50 mm) (that is, a test piece before immersion) was added to a 4% aqueous solution (aqueous solution temperature 25 ° C.) of the polymer 1 obtained in Synthesis Example 1. After soaking for 60 minutes, it was dried at 130 ° C. for 60 minutes, and this was referred to as a "test piece after immersion". The amount (%) of the polymer adsorbed on the polyimide membrane was calculated from the change in the weight of the test piece before and after immersion. The results are shown in Table 1. The same evaluation can be performed with an aromatic polyamide-based RO membrane such as the flat sheet membrane SWC5 (manufactured by Nitto Denko KK).
＜実施例２～４、参考例１～２＞
実施例１において、重合体１を表１の通り重合体２～６とした以外は、実施例１と同様の手順にて、吸着率（％）を算出した。結果を表１に記載する。
<Examples 2 to 4, reference examples 1 to 2>
In Example 1, the adsorption rate (%) was calculated by the same procedure as in Example 1 except that the polymer 1 was the polymer 2 to 6 as shown in Table 1. The results are shown in Table 1.
表１の結果から、本発明のファウリング抑制能付与剤は、ＲＯ膜に対する付着力が高いことが確認された。すなわち、本発明のファウリング抑制能付与剤は親水性であり、かつＲＯ膜に対する親和性が高い為、良好なファウリング抑制能を発現することが明らかとなった。 From the results in Table 1, it was confirmed that the fouling inhibitory ability-imparting agent of the present invention has a high adhesive force to the RO membrane. That is, it was clarified that the fouling-suppressing ability-imparting agent of the present invention exhibits a good fouling-suppressing ability because it is hydrophilic and has a high affinity for RO membranes.
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| JP2016511288A (en) | 2012-12-17 | 2016-04-14 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Membrane with improved flux and method for producing said membrane |
| WO2016166084A1 (en) | 2015-04-13 | 2016-10-20 | Basf Se | Processes for reducing the fouling of surfaces |
| JP2017000998A (en) | 2015-06-15 | 2017-01-05 | 学校法人五島育英会 | Fouling inhibitor, porous filtration membrane for water treatment and production method of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016511288A (en) | 2012-12-17 | 2016-04-14 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Membrane with improved flux and method for producing said membrane |
| JP2014144394A (en) | 2013-01-28 | 2014-08-14 | Nof Corp | Fouling inhibitor composition for porous filtration film, porous filtration film and manufacturing method thereof |
| WO2016166084A1 (en) | 2015-04-13 | 2016-10-20 | Basf Se | Processes for reducing the fouling of surfaces |
| JP2017000998A (en) | 2015-06-15 | 2017-01-05 | 学校法人五島育英会 | Fouling inhibitor, porous filtration membrane for water treatment and production method of the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2020178892A1 (en) * | 2019-03-01 | 2021-12-16 | ナンヤン テクノロジカル ユニヴァーシティー | Fowling inhibitory ability-imparting agent and water treatment membrane using it |
| JP7256505B2 (en) | 2019-03-01 | 2023-04-12 | ナンヤン テクノロジカル ユニヴァーシティー | Anti-fouling agent and water treatment membrane using the same |
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| JP2019042689A (en) | 2019-03-22 |
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