JPH03275740A - Production of cellular polyamide - Google Patents
Production of cellular polyamideInfo
- Publication number
- JPH03275740A JPH03275740A JP7557190A JP7557190A JPH03275740A JP H03275740 A JPH03275740 A JP H03275740A JP 7557190 A JP7557190 A JP 7557190A JP 7557190 A JP7557190 A JP 7557190A JP H03275740 A JPH03275740 A JP H03275740A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- solvent
- solvents
- surface area
- gel
- 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
- 239000004952 Polyamide Substances 0.000 title claims abstract description 34
- 229920002647 polyamide Polymers 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 230000001413 cellular effect Effects 0.000 title abstract 3
- 239000002904 solvent Substances 0.000 claims abstract description 46
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 229920002292 Nylon 6 Polymers 0.000 abstract description 3
- 229920002302 Nylon 6,6 Polymers 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- KDISMIMTGUMORD-UHFFFAOYSA-N 1-acetylpiperidine Chemical compound CC(=O)N1CCCCC1 KDISMIMTGUMORD-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- KYWXRBNOYGGPIZ-UHFFFAOYSA-N 1-morpholin-4-ylethanone Chemical compound CC(=O)N1CCOCC1 KYWXRBNOYGGPIZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- FILVIKOEJGORQS-UHFFFAOYSA-N 1,5-dimethylpyrrolidin-2-one Chemical compound CC1CCC(=O)N1C FILVIKOEJGORQS-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229940117955 isoamyl acetate Drugs 0.000 description 3
- -1 polyhexamethylene sebacamide Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- RHLBOBPOIZROJX-UHFFFAOYSA-N 1-acetylpyrrolidine-2,5-dione Chemical compound CC(=O)N1C(=O)CCC1=O RHLBOBPOIZROJX-UHFFFAOYSA-N 0.000 description 2
- KYEACNNYFNZCST-UHFFFAOYSA-N 1-methylpyrrolidine-2,5-dione Chemical compound CN1C(=O)CCC1=O KYEACNNYFNZCST-UHFFFAOYSA-N 0.000 description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- YLHUPYSUKYAIBW-UHFFFAOYSA-N 1-acetylpyrrolidin-2-one Chemical compound CC(=O)N1CCCC1=O YLHUPYSUKYAIBW-UHFFFAOYSA-N 0.000 description 1
- VUQMOERHEHTWPE-UHFFFAOYSA-N 1-ethylpiperidin-2-one Chemical compound CCN1CCCCC1=O VUQMOERHEHTWPE-UHFFFAOYSA-N 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- LNWWQYYLZVZXKS-UHFFFAOYSA-N 1-pyrrolidin-1-ylethanone Chemical compound CC(=O)N1CCCC1 LNWWQYYLZVZXKS-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 241001197925 Theila Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- MGDNHIJGIWHQBL-UHFFFAOYSA-N n-ethyl-n-methylacetamide Chemical compound CCN(C)C(C)=O MGDNHIJGIWHQBL-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は多孔性ポリアミドの製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing porous polyamide.
更に詳しくは、濾過材料、機能性材料などの担体など、
または重合用のプレポリマーなどに用いる多孔性ポリア
ミドの製造方法に関する。More specifically, carriers such as filtration materials and functional materials,
The present invention also relates to a method for producing porous polyamide used as a prepolymer for polymerization.
従来、多孔性ポリアミドを製造する方法としては、「高
分子」第23巻、第592〜596頁(1974)に記
載されているように、ポリマーを塩化カルシウム/メタ
ノール溶媒に溶解した後、溶液を板上に流延し溶媒を蒸
発し、凝固させ、水中で塩を溶出することによる溶液凝
固方法が知られている。Conventionally, as a method for producing porous polyamide, as described in "Kobunshi" Vol. 23, pp. 592-596 (1974), a polymer is dissolved in a calcium chloride/methanol solvent, and then the solution is dissolved. A solution coagulation method is known in which the solution is cast on a plate, the solvent is evaporated, the solution is coagulated, and the salt is eluted in water.
また、特開平1−245035号公報には上記の方法を
改良した方法が開示されている。つまり、ポリマーとと
もに水溶性の塩を塩化カルシウム/メタノール溶媒に溶
解し、吸湿させてから溶液凝固することにより多孔質膜
を調製する方法である。Further, Japanese Patent Application Laid-Open No. 1-245035 discloses a method that is an improvement on the above method. That is, a porous membrane is prepared by dissolving a water-soluble salt together with a polymer in a calcium chloride/methanol solvent, absorbing moisture, and coagulating the solution.
しかしながら、「高分子」に記載されているような溶液
凝固法で得られる多孔性ポリマーは、特開平1−245
035号公報に開示されているような連続の多孔構造を
もたず、孤立孔の集合構造となる。However, porous polymers obtained by a solution coagulation method as described in "Polymer" are
It does not have a continuous porous structure as disclosed in Japanese Patent No. 035, but has an aggregated structure of isolated pores.
従って、表面積も0.oi rri’/gと非常に小さ
いものであると推定できる。Therefore, the surface area is also 0. It can be estimated that it is very small, oi rri'/g.
また、特開平1−245035号公報に記載の方法では
、塩が沈澱する部分のみが連続多孔構造となり、他の部
分は、孤立孔の集合構造となる。従って、この膜の表面
積も0.1rrr/g程度と推定され表面積の小さいも
のである。Further, in the method described in JP-A-1-245035, only the portion where the salt is precipitated has a continuous porous structure, and the other portions have an aggregated structure of isolated pores. Therefore, the surface area of this film is estimated to be about 0.1rrr/g, which is a small surface area.
本発明は、表面積の大きい多孔性ポリアミドを提供する
ことにある。The object of the present invention is to provide a porous polyamide with a large surface area.
すなわち、本発明は、ポリアミドを溶媒に溶解した後ゲ
ル化し、このゲルの網目構造を崩さないようにこのゲル
から溶媒を除去することを特徴とする多孔性ポリアミド
の製造方法、である。That is, the present invention is a method for producing porous polyamide, which is characterized by dissolving polyamide in a solvent, gelling it, and removing the solvent from the gel without destroying the network structure of the gel.
本発明に係るポリアミドは、ポリヘキサメチレンアジパ
ミド(ナイロン66)、ポリカプラミド(ナイロン6)
、ポリウンデカノアミド(ナイロン11) 、ポリへキ
サメチレンセバカミド(ナイロン61O)、ポリテトラ
メチレンアジパミド(ナイロン46)、ポリウンデカメ
チレンアジパミド(ナイロン116)などの脂肪族系ポ
リアミドまたは、これらの二種以上を組み合わせてなる
ポリアミドである。また、このポリアミドは、15wt
%以下の他のポリマーを含む共重合または混合物であっ
てもよい。The polyamide according to the present invention includes polyhexamethylene adipamide (nylon 66), polycapramide (nylon 6)
, polyundecanoamide (nylon 11), polyhexamethylene sebacamide (nylon 61O), polytetramethylene adipamide (nylon 46), polyundecamethylene adipamide (nylon 116), and other aliphatic polyamides Alternatively, it is a polyamide formed by combining two or more of these types. Moreover, this polyamide has a weight of 15wt.
It may also be a copolymer or mixture containing up to % of other polymers.
本発明に係るポリアミドは必要に応じて熱安定剤、酸化
防止剤、光安定剤、顔料、触媒、艶消し剤などの添加剤
を配合してもよい。The polyamide according to the present invention may contain additives such as a heat stabilizer, an antioxidant, a light stabilizer, a pigment, a catalyst, and a matting agent, if necessary.
本発明に係るポリアミドの数平均分子量は、特に制限さ
れるものではない。The number average molecular weight of the polyamide according to the present invention is not particularly limited.
次に本発明のポリアミドの表面積をIn(/g以上、好
ましくは1r11′/g〜100 rrr/gの多孔性
にする製造方法の一つを具体的に説明する。Next, one of the manufacturing methods for making the polyamide of the present invention porous with a surface area of In(/g or more, preferably 1r11'/g to 100 rrr/g) will be specifically explained.
まず、ポリアミドを溶媒に加熱溶解し、均一な溶液とす
る。First, polyamide is heated and dissolved in a solvent to form a uniform solution.
本発明に用いる溶媒は、ポリアミドを溶解し得るもので
あれば何でもよい。例えば、次に示す溶媒または、これ
らの溶媒と塩とを組み合わせて使用できる。The solvent used in the present invention may be any solvent as long as it can dissolve the polyamide. For example, the following solvents or a combination of these solvents and salts can be used.
すなわち、N−メチル−2−ピロリドン、Nエチル−2
−ピロリドン、N−メチル−ピペリドン、N−エチル−
ピペリドン、N、N−ジメチルアセトアミド、N−メチ
ル−N−エチルアセトアミド、N、 N−ジエチルア
セトアミド、N−アセチルピペリジン、N−アセチルピ
ロリジン、N−アセチルモルフォリン、N−アセチルピ
ロリドン、N−アセチルピペリドン、1,5−ジメチル
ピロリジノンなどのアミド系溶媒、1.3−ジメチル−
2−イミダゾリジノン、1,3−ジメチル−4,5,6
(H)−2−ピリミジノン、テトラメチルウレアなどの
ウレア系溶媒、N−メチルコハク酸イミド、N−アセチ
ルコハク酸イミドなとのイミド系溶媒、テトラヒドロフ
ランなどのエーテル系溶媒、メタノール、エタノール、
ベンジルアルコール、フルフリルアルコールなどのアル
コール系溶媒、フェノール、オルトクロロフェノール、
m−クレゾールなどのフェノール系溶媒、蟻酸、硫酸、
トリクロロ酢酸などの酸系溶媒、ヘキサフロオロイソプ
ロパノール、ヘキサフルオロアセトンなどの弗素系溶媒
などからなる群の中から選ばれる一種または複数の溶媒
からなる溶媒である。That is, N-methyl-2-pyrrolidone, N-ethyl-2
-pyrrolidone, N-methyl-piperidone, N-ethyl-
Piperidone, N,N-dimethylacetamide, N-methyl-N-ethylacetamide, N,N-diethylacetamide, N-acetylpiperidine, N-acetylpyrrolidine, N-acetylmorpholine, N-acetylpyrrolidone, N-acetylpipe Lydone, amide solvents such as 1,5-dimethylpyrrolidinone, 1,3-dimethyl-
2-imidazolidinone, 1,3-dimethyl-4,5,6
(H)-2-pyrimidinone, urea solvents such as tetramethylurea, imide solvents such as N-methylsuccinimide and N-acetylsuccinimide, ether solvents such as tetrahydrofuran, methanol, ethanol,
Alcohol solvents such as benzyl alcohol and furfuryl alcohol, phenol, orthochlorophenol,
Phenolic solvents such as m-cresol, formic acid, sulfuric acid,
The solvent is one or more solvents selected from the group consisting of acid solvents such as trichloroacetic acid, fluorine solvents such as hexafluoroisopropanol, and hexafluoroacetone.
上記溶媒のなかで好ましいものは、ポリアミド重合体を
溶解するときに、ポリマーの分解をひき起こしにくいア
ミド系溶媒、ウレア系溶媒、イミド系溶媒、アルコール
系溶媒である。Among the above solvents, preferred are amide solvents, urea solvents, imide solvents, and alcohol solvents that do not easily cause decomposition of the polyamide polymer when it is dissolved therein.
なかでも、N−メチル−2−ピロリドン、N−エチル−
2−ピロリドン、1,5−ジメチルピロリジノン、N−
アセチルピペリジン、N−アセチルモルフォリン、1,
3−ジメチル−2−イミダゾリジノン、1,3−ジメチ
ル−4,5,6(H) −2−ピリミジノン、N−メチ
ルコハク酸イミド、N−アセチルコハク酸イミド、メタ
ノール、エタノールからなる溶媒系が、ポリアミドの溶
解能力が高いので更に好ましい。Among them, N-methyl-2-pyrrolidone, N-ethyl-
2-pyrrolidone, 1,5-dimethylpyrrolidinone, N-
Acetylpiperidine, N-acetylmorpholine, 1,
A solvent system consisting of 3-dimethyl-2-imidazolidinone, 1,3-dimethyl-4,5,6(H)-2-pyrimidinone, N-methylsuccinimide, N-acetylsuccinimide, methanol, and ethanol was used. , is more preferred since it has a high ability to dissolve polyamide.
また更になかでも最も好ましいものは、N−メチル−2
−ピロリドン、1,5−ジメチル−2−ピロリジノン、
N−アセチルピペリジン、N−アセチルモルフォリン、
1.3−ジメチル−2−イミダゾリジノンおよび1.3
−ジメチル−4,5,6(H)−2−ピリミジノンであ
る。更に好適には、N−メチル−2−ピロリドン、N−
アセチルピペリジン、N−アセチルモルフォリンおよび
1.3−ジメチル−2−イミダゾリジノンである。Furthermore, the most preferable one is N-methyl-2
-pyrrolidone, 1,5-dimethyl-2-pyrrolidinone,
N-acetylpiperidine, N-acetylmorpholine,
1.3-dimethyl-2-imidazolidinone and 1.3
-dimethyl-4,5,6(H)-2-pyrimidinone. More preferably, N-methyl-2-pyrrolidone, N-
Acetylpiperidine, N-acetylmorpholine and 1,3-dimethyl-2-imidazolidinone.
また、本発明に用いる塩は、周期表のIa族、Ib族、
Ila族、nb族、IIIa族、■族元素のハロゲン化
物、または過ハロゲン化物であって、この塩とともに用
いる溶媒にも可溶でなければならない。In addition, the salts used in the present invention include group Ia, group Ib of the periodic table,
It is a halide or perhalide of an element of the Ila group, the Nb group, the IIIa group, or the Group Ⅰ, and must also be soluble in the solvent used together with the salt.
好ましい塩は、リチウム、カルシウム、マグネシウム、
亜鉛、アルミニウム、硼素、および鉄のハロゲン化物、
または過ハロゲン化物である。Preferred salts are lithium, calcium, magnesium,
halides of zinc, aluminum, boron, and iron,
or perhalide.
塩の作用としては、ポリマーの溶媒への溶解性の向上、
溶液のゲル化温度の低下などが期待できる。The effects of salts include improving the solubility of polymers in solvents,
A decrease in the gelation temperature of the solution can be expected.
このため、塩は、ポリアミドのアミド基に対して、O〜
100moA/mol添加する。好ましくは、0、 O
1〜60 mo 12 /mo I! 、更に好ましく
は、0.05〜2moj2/moA、もっとも好適には
、0.1〜1mof/mof添加する。Therefore, the salt has O to amide groups of polyamide.
Add 100 moA/mol. Preferably 0, O
1~60 mo 12 /mo I! , more preferably 0.05 to 2 moj2/moA, most preferably 0.1 to 1 moj2/moA.
前記の溶媒にポリアミド重合体を加え、この重合体が溶
解する温度で加熱溶解して、原液を調製する。この際、
溶媒、塩、ポリマーは使用前に脱水、乾燥し、その水分
率を極力少なくしておくことが好ましい。そして、溶解
操作も乾燥窒素中などで行うのが好ましい。なぜなら、
溶解時の温度が高い場合には、加熱によりポリマーが加
水分解し、分子量の低下を起すからである。A stock solution is prepared by adding a polyamide polymer to the above solvent and dissolving it by heating at a temperature at which the polymer dissolves. On this occasion,
It is preferable that the solvent, salt, and polymer be dehydrated and dried before use to keep their moisture content as low as possible. The dissolution operation is also preferably carried out in dry nitrogen. because,
This is because if the temperature at the time of dissolution is high, the polymer will be hydrolyzed by heating, resulting in a decrease in molecular weight.
溶解は、ヘリカル翼やニーダ−などを用いである程度の
剪断をかけて溶解するのがよい。ただし、剪断力が強す
ぎるとポリマーの分子鎖を切断するため好ましくない。For melting, it is preferable to apply a certain amount of shear using a helical blade, a kneader, or the like. However, if the shearing force is too strong, the molecular chains of the polymer will be cut, which is not preferable.
本発明の方法ではポリアミドと溶媒との重量比が、多孔
性ポリアミドの表面積に影響を与えるので、求める表面
積によりその割合を調整することが好ましい。なお使用
するポリアミドの分子量によってゲル化する範囲が変化
するが、ポリアミドは通常0.1〜60wt%であり、
好ましくは0.5〜30wt%である。更に好ましくは
1〜15wt%である。In the method of the present invention, the weight ratio of polyamide and solvent affects the surface area of the porous polyamide, so it is preferable to adjust the ratio depending on the desired surface area. Note that the range of gelation varies depending on the molecular weight of the polyamide used, but the polyamide is usually 0.1 to 60 wt%,
Preferably it is 0.5 to 30 wt%. More preferably, it is 1 to 15 wt%.
ついで、この溶液をガラス板などの板上に流延するかま
たは、ガラス板の間に挟んだ後、ゲル化する温度まで冷
却し固化させる。このように固化させたゲルは、網目構
造を有するものとなる。Next, this solution is cast onto a plate such as a glass plate or sandwiched between glass plates, and then cooled to a gelling temperature and solidified. The gel thus solidified has a network structure.
本発明の方法は次に、このゲルから実質的に網目構造を
壊さないように、溶媒を除去することが必要である。The method of the invention then requires removing the solvent from this gel without substantially disrupting the network structure.
溶媒を除去する方法としては、蒸発により除去するか、
またはこの溶媒系を溶解する別の溶媒を用いてこの溶媒
系を抽出する方法などが好ましく用いられる。The solvent can be removed by evaporation,
Alternatively, a method of extracting this solvent system using another solvent that dissolves this solvent system is preferably used.
しかし、表面張力の大きい溶媒の場合には、蒸発すると
きに、網目構造を崩してしまうことがある。このような
場合には、−旦表面張力の小さい溶媒に置き換えてから
蒸発させるかまたは臨界点を利用して乾燥するとよい。However, in the case of a solvent with a high surface tension, the network structure may be disrupted during evaporation. In such a case, it is preferable to first replace the solvent with a solvent having a lower surface tension and then evaporate it or dry it using a critical point.
例えば、溶媒を液体二酸化炭素で置換した後、臨界点以
上の温度圧力、例えば、35℃、73気圧以上の条件下
で、液体二酸化炭素を気化することにより、網目構造を
維持したまま溶媒を除去することができる。For example, after replacing the solvent with liquid carbon dioxide, the solvent is removed while maintaining the network structure by vaporizing the liquid carbon dioxide at a temperature and pressure above the critical point, e.g., 35°C and 73 atm or above. can do.
このようにして、表面積の大きい多孔性ポリアミドが得
られる。In this way, a porous polyamide with a large surface area is obtained.
以下、本発明を実施例により説明する。なお物性の測定
は次の方法で行った。The present invention will be explained below using examples. The physical properties were measured using the following method.
表面積の測定(BET法)
島津製作所製、流動式比表面積自動測定装置(商品名、
フローソーブ2300型)を用いて、−点法で測定した
。Measurement of surface area (BET method) Manufactured by Shimadzu Corporation, flow type automatic specific surface area measuring device (product name,
It was measured by the -point method using a Flowsorb Model 2300).
試料1.0gをセルに入れ、200℃XIO分間、脱気
処理したのち、N2/Heの30mon%混合ガスを用
いて測定した。1.0 g of the sample was placed in a cell and degassed at 200° C. for XIO minutes, followed by measurement using a 30 mon% mixed gas of N2/He.
実施例1
50%へキサメチレンアジベイト(以下AH塩という)
水溶液を反応容器にいれ、充分に窒素置換した後、この
反応容器を密閉した。この反応容器を290℃に加熱し
た。容器内の圧力が17.5kg / ciになるよう
に蒸気を抜きながら1時間反応させた後、徐々に圧力を
大気圧にした。これにより、数平均分子量15000の
ポリマーを得た。Example 1 50% hexamethylene adibate (hereinafter referred to as AH salt)
The aqueous solution was put into a reaction vessel, and after the atmosphere was sufficiently purged with nitrogen, the reaction vessel was sealed. The reaction vessel was heated to 290°C. After reacting for 1 hour while removing steam so that the pressure inside the container was 17.5 kg/ci, the pressure was gradually raised to atmospheric pressure. As a result, a polymer having a number average molecular weight of 15,000 was obtained.
このポリマー15wt%をN−メチル−2−ピロリドン
(以下NMPという)に190℃で溶解し均一な溶液と
した。この溶液を室温まで冷却したところ、固化しゲル
となった。このゲルを酢酸イソアミルに浸漬し、NMP
を酢酸イソアミルで充分に置換した。この酢酸イソアミ
ルで置換したゲルを乾燥しないように留意しながら一1
o℃で液体二酸化炭素に浸漬し密閉した。ついで20’
Cにして20分間放置し、充分に液体二酸化炭素に置換
させた後35℃にした。このときの圧力は73気圧を示
していた。この条件ではすでに臨界点を越えているので
液体二酸化炭素は気化している。15 wt% of this polymer was dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) at 190°C to form a uniform solution. When this solution was cooled to room temperature, it solidified into a gel. This gel was immersed in isoamyl acetate and NMP
was fully substituted with isoamyl acetate. While being careful not to dry the gel substituted with isoamyl acetate,
It was immersed in liquid carbon dioxide at 0°C and sealed. Then 20'
C and left for 20 minutes, and after being sufficiently replaced with liquid carbon dioxide, the temperature was raised to 35°C. The pressure at this time was 73 atmospheres. Under these conditions, the critical point has already been exceeded, so the liquid carbon dioxide has vaporized.
この状態に5分間放置した後、300mon/分の速度
で二酸化炭素を排出した。このようにして、多孔性ポリ
マーが得られた。After leaving this state for 5 minutes, carbon dioxide was discharged at a rate of 300 mon/min. In this way, a porous polymer was obtained.
この多孔性ポリマーの表面積をBET法で測定したとこ
ろ、14rrr/gであった。The surface area of this porous polymer was measured by the BET method and was found to be 14 rrr/g.
本発明によると、連続した孔を有する多孔性ポリアミド
を得ることができる。気体の通気性、液体の通液性およ
びポリアミドの化学構造特性の十分な利用ができる。従
って、フィルターや機能性物質の固定担体材料などの用
途に使用が可能である。According to the present invention, a porous polyamide having continuous pores can be obtained. Gas permeability, liquid permeability, and chemical structural characteristics of polyamide can be fully utilized. Therefore, it can be used for applications such as filters and immobilized carrier materials for functional substances.
Claims (1)
の網目構造を崩さないようにこのゲルから溶媒を除去す
ることを特徴とする多孔性ポリアミドの製造方法。1. A method for producing porous polyamide, which comprises dissolving polyamide in a solvent, gelling it, and removing the solvent from the gel without destroying the network structure of the gel.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7557190A JPH03275740A (en) | 1990-03-27 | 1990-03-27 | Production of cellular polyamide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7557190A JPH03275740A (en) | 1990-03-27 | 1990-03-27 | Production of cellular polyamide |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03275740A true JPH03275740A (en) | 1991-12-06 |
Family
ID=13580002
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7557190A Pending JPH03275740A (en) | 1990-03-27 | 1990-03-27 | Production of cellular polyamide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03275740A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006082006A (en) * | 2004-09-16 | 2006-03-30 | Daicel Chem Ind Ltd | Filter material and manufacturing method therefor |
JP2007254577A (en) * | 2006-03-23 | 2007-10-04 | Gunma Univ | Polyamide porous membrane and method for producing the same |
-
1990
- 1990-03-27 JP JP7557190A patent/JPH03275740A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006082006A (en) * | 2004-09-16 | 2006-03-30 | Daicel Chem Ind Ltd | Filter material and manufacturing method therefor |
JP2007254577A (en) * | 2006-03-23 | 2007-10-04 | Gunma Univ | Polyamide porous membrane and method for producing the same |
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