JP4129655B2 - Manufacturing method of polyamide filter - Google Patents
Manufacturing method of polyamide filter Download PDFInfo
- Publication number
- JP4129655B2 JP4129655B2 JP02487899A JP2487899A JP4129655B2 JP 4129655 B2 JP4129655 B2 JP 4129655B2 JP 02487899 A JP02487899 A JP 02487899A JP 2487899 A JP2487899 A JP 2487899A JP 4129655 B2 JP4129655 B2 JP 4129655B2
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- JP
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- Prior art keywords
- polyamide
- glass
- water
- composite
- pulp
- 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.)
- Expired - Fee Related
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- Compositions Of Macromolecular Compounds (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は耐熱性に優れるガラスとポリアミドとの均一な複合体から成るポリアミド系フィルターの製造方法に関する。
【0002】
【従来の技術】
ポリアミドから成るフィルター材料は、例えば、特開昭61−149217号公報に記載されている。これらのポリアミドを構成要素とするフィルターは、耐薬品性に優れ、無機フィルターに比し軽量であるが、基本的に高温域で熱変形するために、例えば300℃以上の温度では使用しづらい問題があった。
【0003】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、300℃以上の温度でも熱変形しないポリアミド系フィルターを提供することにある。
【0004】
【課題を解決するための手段】
本発明者らは、ガラスとポリアミドとの均一な複合体のパルプ状粒子を部分的に融着させることにより、上記課題が達せられることを見いだし、本発明を完成するに至った。
【0005】
即ち、本発明は、ジアミンと水ガラスと水とを必須成分とする水溶液(A)と、ジカルボン酸ハライドと有機溶媒とを必須成分とする有機溶液(B)とを接触させて得た、ガラスとポリアミドの均一な複合体のパルプ状粒子(C)を抄造し、次いで該パルプ状粒子(C)間を接着させることを特徴とするポリアミド系フィルターの製法である。
【0006】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明で用いる、ガラスとポリアミドとの均一な複合体から成るパルプ粒子(C)は、本発明者らが既に開示した方法、例えば、特開平10−176106号公報に開示した製法により得られる。この製法では、ジアミンと水ガラスと水とを必須成分とする水溶液(A)と、ジカルボン酸ハライドと有機溶媒とを必須成分とする有機溶液(B)とを接触させ、ジアミンとジカルボン酸ハライド間の重縮合によりポリアミドが常温で殆ど瞬時に得られる。
【0007】
ジアミンと水ガラスと水とを必須成分とする水溶液(A)に含まれるジアミンとしては、1,3−ジアミノプロパン、1,4ージアミノブタン、1,5ージアミノペンタン、1,6−ジアミノヘキサン、m−キシリレンジアミン、p−キシリレンジアミンといった脂肪族鎖を有するジアミンや、
【0008】
2,5−ノルボルナンジアミン、2,6−ノルボルナンジアミン等の脂環式ジアミンや、m−フェニレンジアミン、p−フェニレンジアミン、1,5’−ジアミノナフタレン、1,8−ジアミノナフタレン、2,3−ジアミノナフタレン、3,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルエーテル、
【0009】
3,4’−ジアミノジフェニルスルホン、4,4’−ジアミノジフェニルスルホン、3,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルメタン、及びこれらの芳香族環の一個以上の水素をハロゲン、ニトロ基、又はアルキル基で置換した全芳香族ジアミンを挙げることができ、なかでも 1,6−ジアミノヘキサン、m−キシリレンジアミン、m−フェニレンジアミンが好ましい。
【0010】
(A)中の水ガラスは、その化学組成がM2O・nSiO2で表現される(M=アルカリ金属)水溶性のガラスであり、例えば日本工業規格(JIS K1408−1950)に記載の水ガラス1号、2号、3号、4号といった予め水に溶解せしめた水ガラス(M=がナトリウムであり、1.2≦n≦4である)を使用することが出来る。
【0011】
水ガラスの濃度としては固型分基準で2〜240g/L(L=リットル)の範囲が挙げられ、複合体中のガラスの含有率はガラスの濃度を調製することにより制御することが可能である。この他、重縮合反応を十分に促進させる目的で、水酸化ナトリウム等の酸受容体及び/又はラウリル硫酸ナトリウム等の界面活性剤が添加されてもよい。
【0012】
ジカルボン酸ハライドと有機溶媒とを必須成分とする有機溶液(B)に用いる有機溶媒としてはトルエン、キシレン、メチルイソブチルケトン、クロロホルム、シクロヘキサン、シクロヘキサノン、テトラヒドロフランを代表的な例として挙げることが出来、ジカルボン酸ハライドとしては、塩化アジポイル、塩化アゼラオイル、塩化テレフタロイル、塩化イソフタロイルを挙げることができる。
【0013】
(A)と(B)との接触による水ガラスのポリアミドへの複合化において、水ガラス自身の反応が進行し、アリカリ金属成分の極めて少ない良質のシリカ型のガラスとしてポリアミド中に均一に取り込まれる。ここでいう接触とは、(A)と(B)の2液が混ざらずにその界面で接触する場合と混ざり合う場合との双方を含む。
【0014】
該製法で得られる複合体中に生成するガラスの平均粒径は10〜300nmと極めて微細で、ポリアミドとの接着性も良好である。また複合体中のガラス含有量は、モノマー(ジアミン、ジカルボン酸のハライド)及び/又は水ガラス濃度を調節することにより、複合体中のガラス含有率5〜70重量%の範囲で制御可能である。
【0015】
(A)及び(B)中のモノマー濃度が0.4〜0.8モル/Lの範囲で、複合体を製造した場合は、得られる複合体の繊維質が絡み合いを生じ易く、抄造性の良好な複合体のパルプ状粒子(C)が得易い。しかし、重合反応終了時に抄造性の少ない複合体が得られた場合であっても、該複合体と純ポリアミドとをその良溶媒中から共沈させることにより、抄造性を有するパルプ粒子状の複合体を得ることが出来る。
【0016】
得られたパルプ粒子は、必要に応じて水や有機溶媒で洗浄してから水等に分散させ、次いで網型に配しポンプ等で水を吸引除去して抄造した後に乾燥して、シートもしくはフィルムに成形される。得られたシートもしくはフィルムは、少なくとも部分的にパルプ粒子間が接着されたものとなる。これは、生成直後のパルプ粒子はゲル様の物質であるが、洗浄、乾燥する過程で固形になる際に強固な接着がなされるためである。
【0017】
該シートもしくはフィルムを加圧処理して、その空隙率を0.1〜0.9の範囲で制御することにより本発明のポリアミド系フィルターを製造することが出来る。一般に加圧処理圧が高いほど、空隙率は低くなり、フィルターの強度は増加するが、ろ過特性は低下する傾向にあり、用途に応じて適宜、処理圧を選定し、空隙率を制御することが好ましい。
【0018】
【実施例】
以下、本発明を実施例にて説明するが、これはあくまでも本発明の代表的態様を例示するものであり、本発明はこれに限定されるものではない。
【0019】
(実施例1)
水ガラス1.50gと1,6−ジアミノヘキサン4.64gに室温で蒸留水を加えながら攪拌し、均一透明な300mLの水溶液を調製した。また、塩化アジポイル7.32gに室温でトルエンを加えて攪拌し、均一透明な200mLの有機溶液を調製した。次いで1Lの容量のブレンダー瓶(Osterizer製)に水溶液相を入れ、付属の攪拌羽根で毎分10000回転で攪拌しながら、25℃にて有機溶液を一度に加えた。
【0020】
混合溶液から直ちに複合体のパルプ粒子状(ポリアミド成分=ナイロン66、灰分=61重量%)が析出した。懸濁状態のまま2分間攪拌を続けた。得られた複合体を濾別した後、沸騰アセトン、次いで蒸留水で洗浄し、蒸留水に分散して分散液を得た。
【0021】
分散液を200メッシュのステンレス網に通じ、5mm厚の平板に抄造した後に乾燥し、ポリアミド系フィルターを製造した。このフィルターの強度は6.1MPa、空隙率は0.90で、ガス中の0.3μmの粒子を効率良く捕集し、且つ350℃で24時間保存しても安定して、その形状を保った。
【0022】
【発明の効果】
本発明は、300℃以上の温度でも熱変形しないポリアミド系フィルターの製法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polyamide filter comprising a uniform composite of glass and polyamide having excellent heat resistance.
[0002]
[Prior art]
A filter material made of polyamide is described in, for example, JP-A-61-149217. These polyamide-based filters have excellent chemical resistance and are lighter in weight than inorganic filters, but are basically difficult to use at temperatures of 300 ° C or higher, for example, because they are thermally deformed at high temperatures. was there.
[0003]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a polyamide filter that does not thermally deform even at a temperature of 300 ° C. or higher.
[0004]
[Means for Solving the Problems]
The present inventors have found that the above problem can be achieved by partially fusing pulp-like particles of a uniform composite of glass and polyamide, and have completed the present invention.
[0005]
That is, the present invention is a glass obtained by contacting an aqueous solution (A) containing diamine, water glass and water as essential components with an organic solution (B) containing dicarboxylic acid halide and an organic solvent as essential components. A method for producing a polyamide-based filter, in which a pulp-like particle (C) of a uniform composite of polyamide and polyamide is made, and then the pulp-like particles (C) are bonded together.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The pulp particles (C) comprising a uniform composite of glass and polyamide used in the present invention can be obtained by the method already disclosed by the present inventors, for example, the production method disclosed in JP-A-10-176106. In this production method, an aqueous solution (A) containing diamine, water glass and water as essential components, and an organic solution (B) containing dicarboxylic acid halide and an organic solvent as essential components are contacted, and the diamine and dicarboxylic acid halide are separated. As a result of the polycondensation, polyamide is obtained almost instantaneously at room temperature.
[0007]
Examples of the diamine contained in the aqueous solution (A) containing diamine, water glass, and water as essential components include 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, m -Diamine having an aliphatic chain such as xylylenediamine and p-xylylenediamine;
[0008]
Alicyclic diamines such as 2,5-norbornanediamine and 2,6-norbornanediamine, m-phenylenediamine, p-phenylenediamine, 1,5′-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3- Diaminonaphthalene, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether,
[0009]
3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and one or more hydrogens of these aromatic rings are halogenated, nitro groups Or a wholly aromatic diamine substituted with an alkyl group, among which 1,6-diaminohexane, m-xylylenediamine, and m-phenylenediamine are preferable.
[0010]
The water glass in (A) is a water-soluble glass whose chemical composition is expressed by M 2 O · nSiO 2 (M = alkali metal), for example, water described in Japanese Industrial Standard (JIS K1408-1950). Water glass (M = is sodium and 1.2 ≦ n ≦ 4) previously dissolved in water such as glass No. 1, No. 2, No. 3, and No. 4 can be used.
[0011]
The concentration of water glass can be in the range of 2 to 240 g / L (L = liter) on a solid basis, and the glass content in the composite can be controlled by adjusting the glass concentration. is there. In addition, for the purpose of sufficiently promoting the polycondensation reaction, an acid acceptor such as sodium hydroxide and / or a surfactant such as sodium lauryl sulfate may be added.
[0012]
Representative examples of the organic solvent used in the organic solution (B) containing a dicarboxylic acid halide and an organic solvent as essential components include toluene, xylene, methyl isobutyl ketone, chloroform, cyclohexane, cyclohexanone, and tetrahydrofuran. Examples of the acid halide include adipoyl chloride, azela oil chloride, terephthaloyl chloride, and isophthaloyl chloride.
[0013]
In the combination of water glass with polyamide by contact with (A) and (B), the reaction of the water glass progresses and is uniformly incorporated into the polyamide as a high-quality silica-type glass with very few ant-kari metal components. . The term “contact” as used herein includes both cases where the two liquids (A) and (B) do not mix and contact at the interface and mix.
[0014]
The average particle size of the glass produced in the composite obtained by the production method is as extremely fine as 10 to 300 nm, and the adhesion to the polyamide is also good. The glass content in the composite can be controlled in the range of 5 to 70% by weight of the glass in the composite by adjusting the monomer (diamine, dicarboxylic acid halide) and / or water glass concentration. .
[0015]
In the case where the monomer concentration in (A) and (B) is in the range of 0.4 to 0.8 mol / L, and the composite is produced, the fiber of the resulting composite is easily entangled, and the papermaking property A good composite pulp-like particle (C) is easy to obtain. However, even when a composite with low papermaking properties is obtained at the end of the polymerization reaction, a pulp particulate composite having papermaking properties can be obtained by coprecipitation of the composite and pure polyamide from the good solvent. You can get a body.
[0016]
The obtained pulp particles are washed with water or an organic solvent as necessary, then dispersed in water, etc., then placed in a net shape and sucked and removed with a pump, etc. Molded into a film. The obtained sheet or film is at least partially bonded between the pulp particles. This is because the pulp particles immediately after the production are gel-like substances, but when they become solid in the process of washing and drying, they are strongly bonded.
[0017]
The polyamide-based filter of the present invention can be produced by pressurizing the sheet or film and controlling the porosity in the range of 0.1 to 0.9. Generally, the higher the pressure treatment pressure, the lower the porosity and the strength of the filter will increase, but the filtration characteristics tend to decrease.Select the treatment pressure appropriately according to the application and control the porosity. Is preferred.
[0018]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, this is only the illustration of the typical aspect of this invention, and this invention is not limited to this.
[0019]
(Example 1)
Stirring while adding distilled water to 1.50 g of water glass and 4.64 g of 1,6-diaminohexane at room temperature, a uniformly transparent 300 mL aqueous solution was prepared. In addition, toluene was added to 7.32 g of adipoyl chloride at room temperature and stirred to prepare a uniform transparent 200 mL organic solution. Subsequently, the aqueous solution phase was put into a 1 L blender bottle (manufactured by Osterizer), and the organic solution was added at 25 ° C. at a time while stirring at 10000 rpm with the attached stirring blade.
[0020]
Immediately from the mixed solution, composite pulp particles (polyamide component = nylon 66, ash content = 61 wt%) were precipitated. Stirring was continued for 2 minutes in a suspended state. The obtained composite was filtered, washed with boiling acetone and then distilled water, and dispersed in distilled water to obtain a dispersion.
[0021]
The dispersion was passed through a 200-mesh stainless steel mesh, formed into a 5 mm-thick flat plate, and then dried to produce a polyamide filter. The strength of this filter is 6.1 MPa, the porosity is 0.90, and 0.3 μm particles in the gas are efficiently collected, and even when stored at 350 ° C. for 24 hours, it remains stable and maintains its shape. It was.
[0022]
【The invention's effect】
The present invention can provide a method for producing a polyamide-based filter that does not thermally deform even at a temperature of 300 ° C. or higher.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP02487899A JP4129655B2 (en) | 1999-02-02 | 1999-02-02 | Manufacturing method of polyamide filter |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP02487899A JP4129655B2 (en) | 1999-02-02 | 1999-02-02 | Manufacturing method of polyamide filter |
Publications (2)
Publication Number | Publication Date |
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JP2000219807A JP2000219807A (en) | 2000-08-08 |
JP4129655B2 true JP4129655B2 (en) | 2008-08-06 |
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JP02487899A Expired - Fee Related JP4129655B2 (en) | 1999-02-02 | 1999-02-02 | Manufacturing method of polyamide filter |
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JP (1) | JP4129655B2 (en) |
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1999
- 1999-02-02 JP JP02487899A patent/JP4129655B2/en not_active Expired - Fee Related
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