JPH0286625A - Manufacture of bismaleimide resin excellent in resistance to organic solvent - Google Patents
Manufacture of bismaleimide resin excellent in resistance to organic solventInfo
- Publication number
- JPH0286625A JPH0286625A JP63238448A JP23844888A JPH0286625A JP H0286625 A JPH0286625 A JP H0286625A JP 63238448 A JP63238448 A JP 63238448A JP 23844888 A JP23844888 A JP 23844888A JP H0286625 A JPH0286625 A JP H0286625A
- Authority
- JP
- Japan
- Prior art keywords
- bismaleimide
- organic solvent
- compound
- cresol
- bismaleimide resin
- 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
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 50
- 239000003960 organic solvent Substances 0.000 title claims abstract description 45
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- -1 bismaleimide compound Chemical class 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- 150000002989 phenols Chemical class 0.000 claims description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 9
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 claims description 7
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- DOJHEVQGYQYOSP-UHFFFAOYSA-N 1-(3-piperazin-1-ylpropyl)piperazine Chemical compound C1CNCCN1CCCN1CCNCC1 DOJHEVQGYQYOSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 42
- 239000002904 solvent Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 2
- 150000002896 organic halogen compounds Chemical class 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 229920000642 polymer Polymers 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000012528 membrane Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 7
- 229930003836 cresol Natural products 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- 101100268135 Caenorhabditis elegans zig-8 gene Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- RCTFHBWTYQOVGJ-UHFFFAOYSA-N chloroform;dichloromethane Chemical compound ClCCl.ClC(Cl)Cl RCTFHBWTYQOVGJ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明は耐有機溶剤性に優れたビスマレイミド樹脂の製
造方法に係り、特に、精密濾過或いは限外症過等の膜材
又は充填剤等に使用され′る耐有機溶剤性樹脂に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for producing bismaleimide resin having excellent organic solvent resistance, and particularly to membrane materials or fillers for microfiltration or ultrafiltration, etc. This invention relates to organic solvent-resistant resins used in
［従来技術］
限外濾過膜或いは選択性透過膜は、コロイド、タンパク
質、微生物等を分散媒から効率良く分離するため、近年
頻繁に利用されている。[Prior Art] Ultrafiltration membranes or selectively permeable membranes have been frequently used in recent years to efficiently separate colloids, proteins, microorganisms, etc. from dispersion media.
このような膜材は工場、ビル等の排水処理に利用され、
更に、食品、医療及び農業の分野にも利用されている。Such membrane materials are used for wastewater treatment in factories, buildings, etc.
Furthermore, it is used in the food, medical and agricultural fields.
限外濾過或いは選択性透過等の膜材に使用される分散媒
は、従来、水溶液であったが、最近の技術の多様化によ
り、水溶液以外の有機溶剤が分散媒として頻繁に使用さ
れる。又、膜材の再生洗浄には有機溶剤が使用されるこ
とがある。このため、膜材は耐有機溶剤性の優れたもの
が望まれている。Dispersion media used in membrane materials for ultrafiltration, selective permeation, etc. have traditionally been aqueous solutions, but with the recent diversification of technology, organic solvents other than aqueous solutions are frequently used as dispersion media. Furthermore, organic solvents are sometimes used for recycling and cleaning membrane materials. For this reason, membrane materials with excellent organic solvent resistance are desired.
また排水処理等に利用される充填材に於いても耐有機溶
剤性を備えた樹脂が望まれている。Furthermore, resins with organic solvent resistance are desired for fillers used in wastewater treatment and the like.
従来、耐有機溶剤性の樹脂としては、フッ素系ポリマー
、光架橋重合物（特開昭５９−１３６１０７、特開昭５
８−８４００６ 、特開昭５９−１１５５４１）が知ら
れている。Conventionally, as organic solvent-resistant resins, fluorine-based polymers, photocrosslinked polymers (JP-A-59-136107, JP-A-5
8-84006, JP-A-59-115541) is known.
［発明が解決しようとする問題点］
しかしながら、光架橋重合物は耐有機溶剤性を有するが
、その重合物を透過膜にした場合、水等の透過性が悪い
ため膜材として好ましくない、また、フッ素系ポリマー
は耐有機溶剤性を有するが、多種の溶媒に対して不溶で
あるため製膜用の溶剤がなく、膜材等の利用を困難にし
ている。[Problems to be solved by the invention] However, although the photocrosslinked polymer has organic solvent resistance, when the polymer is made into a permeable membrane, it is not preferable as a membrane material because of its poor permeability to water, etc. Although fluorine-based polymers have organic solvent resistance, they are insoluble in various solvents, so there is no solvent for film formation, making it difficult to use them as film materials.
また、従来から熱硬化性組成物としてビスマレイミド樹
脂及びその製造方法が知られている。従来のマイレミド
樹脂はビスマレイミドとピペラジンをクレゾール溶媒中
で加熱反応して合成したものであるが、その製造ポリマ
ーは分子量が小さく、クレゾール及びジグ８タン等に溶
解するため耐有機溶剤性がない、また、別のビスマレイ
ミド樹脂の製造方法として、ビスマレイミドとピペラジ
ンとをジクロロメタン或いはＮ−メチルピロリドン溶媒
中で反応させる方法がある（特開昭５Ｏ−１４２７００
）、 Ｌかし、このような溶媒中では、ゲル化が急速に
進む不具合があり、製造ビスマレイミド樹脂は膜材とし
ての利用に適していない。Furthermore, bismaleimide resins and methods for producing the same have been known as thermosetting compositions. Conventional mailemide resin is synthesized by heating and reacting bismaleimide and piperazine in a cresol solvent, but the polymer produced has a small molecular weight and is soluble in cresol and Zig 8 tan, so it has no resistance to organic solvents. In addition, as another method for producing bismaleimide resin, there is a method in which bismaleimide and piperazine are reacted in dichloromethane or N-methylpyrrolidone solvent (Japanese Patent Laid-Open No. 50-142700).
), L However, there is a problem that gelation progresses rapidly in such a solvent, and the produced bismaleimide resin is not suitable for use as a membrane material.
本発明はこのような事情に鑑みて成されたもので、透過
膜材として利用可能な耐有機溶剤性の優れたビスマレイ
ミド樹脂の製造方法を提供することを目的としている。The present invention was made in view of the above circumstances, and an object of the present invention is to provide a method for producing a bismaleimide resin that can be used as a permeable membrane material and has excellent organic solvent resistance.
［問題点を解決するための手段］
本発明は前記も目的を達成するために、どスマレイミト
樹脂の製造に於いて、ビスマレイミド化合物とペルヒド
ロジアザ系複素環化合物とをハロゲン系有機溶媒中で反
応させると共に少量のフェノール類を共存させて反応さ
せることを特徴としている。[Means for Solving the Problems] In order to achieve the above-mentioned objects, the present invention involves reacting a bismaleimide compound and a perhydrodiaza-based heterocyclic compound in a halogenated organic solvent in the production of a dosmaleimide resin. It is characterized by the reaction being carried out in the coexistence of a small amount of phenols.
ビスマレイミド化合物には具体的にＮ、Ｎ’−（４，４
’−シフエルメタン）−ビス−マレイミド等が使用され
、ベルとドロジアザ系複素環化合物にはピペラジン、２
−メチルピペラジン、２．５−ジメチルピラベラジン、
１．４−ペルヒドロジアゼピン（ホモピペラジン） 、
１．３−ジピペラジルプロパン等が使用される。Specifically, the bismaleimide compound contains N, N'-(4,4
'-cyfermethane)-bis-maleimide, etc. are used, and piperazine, 2
-Methylpiperazine, 2,5-dimethylpyratezine,
1.4-perhydrodiazepine (homopiperazine),
1,3-dipiperazylpropane and the like are used.
共存させる前記フェノール類はビスマレイミド化合物に
対して０．５〜２５重量％添加するのが好ましい、フェ
ノール類には具体的にフェノール、ｍ−クレソ゛−ル、
Ｐ−クレゾール、履−インプロビルフェノール、ｐ−イ
ソプロピルフェノール、ハイドロキノン、レソ°ルシン
、カテコール等が使用される。It is preferable that the phenols coexisting are added in an amount of 0.5 to 25% by weight based on the bismaleimide compound.Specifically, the phenols include phenol, m-cresol,
P-cresol, inprovirphenol, p-isopropylphenol, hydroquinone, resolucin, catechol, etc. are used.
［作用コ
本発明に係る耐有機溶剤性に優れたビスマレイミド樹脂
の製造方法によれば、重合反応に於いてハロゲン系有機
溶媒が使用され、この溶媒中には少量のフェノール類が
共存される０反応重合物はフェノール類の少量の共存に
よって急速なゲル化が防止され、膜材、充填材等として
用途性に優れた耐有機溶剤性ポリアミノビスマレイミド
重合体として形成される。[Function] According to the method for producing a bismaleimide resin with excellent organic solvent resistance according to the present invention, a halogenated organic solvent is used in the polymerization reaction, and a small amount of phenols is coexisting in this solvent. The zero-reaction polymer is prevented from rapid gelation by the coexistence of a small amount of phenol, and is formed as an organic solvent-resistant polyamino bismaleimide polymer that has excellent versatility as membrane materials, fillers, etc.
また、従来のようにクレゾール溶媒中での反応でないた
め、得られる反応重合物であるビスマレイミド樹脂は分
子量が大きく、耐有機溶剤性に優れ、メタノール、エタ
ノール、インプロパツール等のアルコール類、アセトン
、メチルエチルケトン等のケトン類、フレオン１１３、
トリクレン等のハロゲン類及びキシレン、ベンゼン等の
芳香族類に対して耐有機溶剤性を有する。In addition, since the reaction is not carried out in a cresol solvent as in conventional methods, the resulting reaction polymer, bismaleimide resin, has a large molecular weight and excellent resistance to organic solvents, including alcohols such as methanol, ethanol, and impropatol, and acetone. , ketones such as methyl ethyl ketone, Freon 113,
It has organic solvent resistance against halogens such as trichlene and aromatics such as xylene and benzene.
更に、本発明に係る対有機溶剤性に優れたビスマレイミ
ド系樹脂は、フッ素ポリマーと相違して可溶溶媒が存在
し、膜材を簡単に製造することができる。Furthermore, unlike fluoropolymers, the bismaleimide resin according to the present invention, which has excellent resistance to organic solvents, has a soluble solvent and can be easily produced into a membrane material.
［発明の好ましい態様］
以下、本発明に係る耐有機溶剤に優れたビスマレイミド
樹脂の製造方法の好ましい態様を詳説する。[Preferred Embodiments of the Invention] Preferred embodiments of the method for producing a bismaleimide resin having excellent organic solvent resistance according to the present invention will be explained in detail below.
耐有機溶剤性に優れたビスマレイミド樹脂は、ビスマレ
イミド化合物とペルヒドロジアザ系複素環化合物とを重
合することにより形成される。該重合反応はハロゲン化
アルキル又は、ハロゲン化アリール等のハロゲン系有機
溶媒中で行われ、ハロゲン系有機溶媒中には、少量のフ
ェノール類が共存される。操作手順としては、ビスマレ
イミド化合物は、ハロゲン系有機溶媒に溶解され、反応
容器内に攪拌状態に置かれる。また、反応容器内にはフ
ェノール類が少量添加される。ペルヒドロジアザ系複素
環化合物はハロゲン系有機溶媒に溶解され、滴下ロート
等により所足時間をかけて室温下で反応容器内に滴下さ
れる。A bismaleimide resin having excellent organic solvent resistance is formed by polymerizing a bismaleimide compound and a perhydrodiaza-based heterocyclic compound. The polymerization reaction is carried out in a halogenated organic solvent such as an alkyl halide or an aryl halide, and a small amount of phenols coexists in the halogenated organic solvent. As for the operating procedure, a bismaleimide compound is dissolved in a halogenated organic solvent and placed in a reaction vessel under stirring. Additionally, a small amount of phenol is added to the reaction vessel. The perhydrodiaza-based heterocyclic compound is dissolved in a halogen-based organic solvent, and is dropped into a reaction vessel at room temperature over a sufficient period of time using a dropping funnel or the like.
本発明において使用されるビスマレイミドとしては、構
造式が、
で表わされる化合物であり１例えばＮ、Ｎ’−ｍ−フェ
ニレンビスマレイミド、Ｎ、Ｎ’−Ｐ−フェニレンビス
マレイミド、 Ｎ、Ｎ’−４，４−ジフェニルメタンビ
スマレイミド、 Ｎ、Ｎ’−４，４−ジフェニルエー
テルビスマレイミド、 Ｎ、Ｎ’−３，４°−ジフェ
ニルエーテルビスマレイミド、 Ｎ、Ｎ’−４，４’−
ジフェニルスルホンビスマレイミド、 Ｎ、Ｎ’−ｍ−
キシレンビスマレイミドなどの化合物が例示される。こ
のビスマレイミドは、ハロゲン系有機溶媒１００ ｇに
対して５ｇ乃至１７ｇの割合で溶解されるのが好ましく
、特に好ましい割合はＬｏｇ乃至１５ｇである。このよ
うな濃度では重合が良好に進行すると共に好適な分子量
の重合体が得られる。The bismaleimide used in the present invention is a compound represented by the following structural formula, such as N,N'-m-phenylenebismaleimide, N,N'-P-phenylenebismaleimide, N,N'- 4,4-diphenylmethane bismaleimide, N,N'-4,4-diphenyl ether bismaleimide, N,N'-3,4°-diphenyl ether bismaleimide, N,N'-4,4'-
Diphenylsulfone bismaleimide, N, N'-m-
Examples include compounds such as xylene bismaleimide. This bismaleimide is preferably dissolved in a ratio of 5g to 17g per 100g of the halogenated organic solvent, and a particularly preferred ratio is Log to 15g. At such a concentration, polymerization proceeds well and a polymer having a suitable molecular weight can be obtained.
フェノール類は少量添加され、その添加量はビスマレイ
ミド化合物１００ ｇに対して０．５ｇ乃至２５ｇであ
る。好ましいフェノール類の添加量は１ｇ乃至１０ｇの
範囲内である。フェノール類の添加量が上記範囲（ビス
マレイミド化合物１００ｇに対して２０．５〜２５ｇの
範囲）にあると得られるビスマレイミド樹脂の分子量が
太きく、耐有機溶剤性の優れたビスマレイミド系樹脂が
得られ、且つ反応溶媒中にゲルが生じないという利点が
ある。Phenols are added in small amounts, and the amount added is 0.5 to 25 g per 100 g of bismaleimide compound. The preferred amount of phenols added is within the range of 1 g to 10 g. When the amount of phenol added is within the above range (20.5 to 25 g per 100 g of bismaleimide compound), the resulting bismaleimide resin has a large molecular weight and has excellent organic solvent resistance. It has the advantage that no gel is formed in the reaction solvent.
本発明で使用されるフェノール類には、フェノール、鳳
−クレソ゛−ル、ｐ−クレソ゛−ル、ＩＩ＋Ｐ−クレゾ
ール混合物、ｍ−イソプロピルフェノール、ｐ−イソプ
ロピルフェノール、ハイドロキノン、レゾルシン、カテ
コール及ｆ／ｌ−’；ｉ’チルハイドロキノン等がある
。この中では、フェノール、層−クレソ゛−ル、ｐ−タ
レゾール及びｍｐ−クレソ゛−ル混合物が好ましい。Phenols used in the present invention include phenol, cresol, p-cresol, II+P-cresol mixture, m-isopropylphenol, p-isopropylphenol, hydroquinone, resorcinol, catechol and f/l-cresol. ';i' Chillhydroquinone, etc. Among these, phenol, layered cresol, p-talesol and mp-cresol mixtures are preferred.
また本発明に使用されるハロゲン系有機溶媒としては、
ジクロロメタン、クロロホルム、四塩化炭素、ジクロロ
エタン、トリクロロエタンクロルベンゼン、ジクロロベ
ンゼン等が好ましい。Further, the halogenated organic solvent used in the present invention includes:
Dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethanechlorobenzene, dichlorobenzene and the like are preferred.
本発明に使用されるペルヒドロジアザ系複素環化合物は
、ハロゲン系有機溶媒で希釈され、滴下溶液とされるが
、その濃度は滴下時間及び容器内の攪拌条件によって適
宜に設定される。The perhydrodiaza-based heterocyclic compound used in the present invention is diluted with a halogen-based organic solvent to form a dropping solution, and the concentration thereof is appropriately set depending on the dropping time and the stirring conditions in the container.
ハロゲン系有機溶媒としては、前記ビスマレイミドの溶
解液と同様な溶媒が好ましい、しかし、同様な溶媒をか
ならず使用する必要はない。As the halogenated organic solvent, it is preferable to use the same solvent as the bismaleimide solution, but it is not always necessary to use the same solvent.
ペルヒドロジアザ系複素環化合物の滴下反応量は、ビス
マレイミド１．０モルに対して０．７６モル乃至１．４
３モルの範囲内で使用されるのが望ましい０本発明にお
いて特に好ましい量は０．９モル乃至１．１モル、最も
好ましくは０．９５〜１．０５モルの範囲内である。The amount of the perhydrodiaza heterocyclic compound added dropwise is 0.76 mol to 1.4 mol per 1.0 mol of bismaleimide.
A particularly preferred amount in the present invention is from 0.9 mol to 1.1 mol, most preferably from 0.95 to 1.05 mol.
ペルヒドロジアザ系複素環化合物は具体的にはピペラジ
ン、２−メチルピペラジン、２．５−ジメルピベラジン
、１．４−ペルヒドロジアゼピン（ホモピペラジン）
、 １．３−ジピペラジルプロパン等がある。Specifically, perhydrodiaza-based heterocyclic compounds include piperazine, 2-methylpiperazine, 2,5-dimelpiverazine, and 1,4-perhydrodiazepine (homopiperazine).
, 1,3-dipiperazylpropane, etc.
本発明の製造方法による耐有機溶剤性ポリアミノビスマ
レイミド樹脂の数平均分子量は７０００以上であること
が好ましく、特に１００００以上の範囲にあることが望
ましい（例えば１００００〜２５０００） 、分子量が
小さいと、クレゾール、ジクロロメタン等に溶解するた
め、ハロゲン系溶剤、芳香族系溶剤に対する耐性が欠け
る０分子量が高分子である場合、メタノール、エタノー
ル、インプロパツール等のアルコール類、アセトン、メ
チルエチルケトン等のケトン類、フレオン１１３、トリ
クレン等のハロゲン類、及びキシレン、ベンゼン等の芳
香族類に対して優れた耐有機溶剤性を有する。The number average molecular weight of the organic solvent-resistant polyamino bismaleimide resin produced by the production method of the present invention is preferably 7,000 or more, particularly preferably in the range of 10,000 or more (for example, 10,000 to 25,000). , dichloromethane, etc., so it lacks resistance to halogenated solvents and aromatic solvents.When the molecular weight is high, alcohols such as methanol, ethanol, and impropatol, ketones such as acetone and methyl ethyl ketone, and freon. It has excellent organic solvent resistance against halogens such as No. 113 and trichlene, and aromatics such as xylene and benzene.
また、この様な製造方法で得られた耐有機溶剤性ポリア
ミノビスマレイミド樹脂には（但し、Ｒ１及びＲ２はア
ルキル鎖、Ｒ３は少なくとも一個のフェニル基を含む二
価の基）の構造部分を含むが、一部分核部分が形成され
ていると考えられ、ビスマレイミド／ペルヒドロジアザ
系複素環化合物のモル比は０．９〜１．１範囲に成るの
が好ましい、ビスマレイミド単位／ペルヒドロジアザ系
複素環化合物単位が上記範囲曾ある場合得られる樹脂は
強靭である。In addition, the organic solvent-resistant polyamino bismaleimide resin obtained by such a production method contains a structural moiety (wherein R1 and R2 are alkyl chains, and R3 is a divalent group containing at least one phenyl group). However, it is thought that a partial core portion is formed, and the molar ratio of bismaleimide/perhydrodiaza heterocyclic compound is preferably in the range of 0.9 to 1.1. is within the above range, the resulting resin is tough.
尚、本発明によって製造された耐有機溶剤性ビスマレイ
ミド樹脂は、ｎ−メチルピロリドン、ジメチルホルムア
ミド、ジメチルアセトアミド等の極性溶媒に可溶なため
、膜材、充填材として簡単に利用できる。The organic solvent-resistant bismaleimide resin produced according to the present invention is soluble in polar solvents such as n-methylpyrrolidone, dimethylformamide, and dimethylacetamide, so it can be easily used as a membrane material or filler.
次に本発明を実施例により更に詳しく説明する。なお、
以下の実施例、比較例においてＧＰＣの分析は次の条件
で分析した。Next, the present invention will be explained in more detail with reference to Examples. In addition,
In the following Examples and Comparative Examples, GPC analysis was performed under the following conditions.
カラム Ａｎ−８００Ｐ＋ Ａｎ−８０Ｍ＋ ＡＤ−８
０３／ｓＸ ２展開液 Ｌｉａｒ Ｏ，０１モル含有
のジメチルホルムアミド
検出器 ２８０ｎｍ（ＵＶ）
標準物質 ポリエチレングリコール
［実施例１］
Ｎ、Ｎ−（４，４ジフエａメタン）−ビスマレイミド（
ＢＭ純度９６％） ６２．３ｇと脂、ｐ−クレゾール混
合物５ｇとをセパラブルフラスコ（１文）に取り、次に
ジクロロメタン４４５ｇを加えて均一な溶液に攪拌する
。Column An-800P+ An-80M+ AD-8
03/sX 2 developing solution Liar O, dimethylformamide containing 01 mol Detector 280 nm (UV) Standard material Polyethylene glycol [Example 1]
62.3 g of BM purity 96%) and 5 g of fat and p-cresol mixture are placed in a separable flask (1 sentence), then 445 g of dichloromethane is added and stirred to form a homogeneous solution.
一方、ピペラジン（試薬特級 純度９９％以上） １
４．５ｇをジクロロメタン２００ｇに溶解し滴下ロート
に入れ、該滴下溶液を前記ＢＭ溶液中に約１時間をかけ
て滴下して室温で反応させる。On the other hand, piperazine (special reagent grade, purity 99% or more) 1
4.5 g of the solution was dissolved in 200 g of dichloromethane and put into a dropping funnel, and the solution was added dropwise to the BM solution over about 1 hour to react at room temperature.
滴下後、略３０分で重合ポリマーが析出し始め、更に一
昼夜攪拌を続ける。次に析出ポリマー中の履、ｐ−クレ
ゾール及びジクロロメタンを除去するため、析出ポリマ
ーを細断する。メタツル中で一日浸漬洗浄後、減圧下で
メタノールを除去してビスマレイミド樹脂（ＰＢＭ−１
）を得た。ＰＢＭ−１のＧＰＣ分析の結果、及び、各種
の溶剤： （アセトン、メチルエチルケトン、メタノー
ル、インプロパツール（ＩＦＡ）、トルエン、タレゾー
ルキシレン、ジクロロメタン、トリクレン）に対する溶
解の有無を調べて表１に示した。The polymer begins to precipitate approximately 30 minutes after dropping, and stirring is continued all day and night. Next, the precipitated polymer is shredded in order to remove the dichloromethane, p-cresol and dichloromethane contained in the precipitated polymer. After washing by immersion in Metatsuru for one day, methanol was removed under reduced pressure and bismaleimide resin (PBM-1
) was obtained. The results of GPC analysis of PBM-1 and the presence or absence of dissolution in various solvents (acetone, methyl ethyl ketone, methanol, inpropatol (IFA), toluene, talezol xylene, dichloromethane, trichlene) are shown in Table 1. Ta.
［実施例２］
Ｎ、Ｎ−（４，４ジフエ匈タンンービスマレイミド（Ｂ
Ｍ純度９６％） ６２．３ｇとｆｆｉ、ｐ−クレゾール
混合物５ｇとをセパラブルフラスコ（ＩＪＩ）に取り、
次にジクロロメタン４４５ｇを加えて均一な溶液に攪拌
する。[Example 2] N,N-(4,4 diphenylene tan-bismaleimide (B
M purity 96%) 62.3g and ffi, p-cresol mixture 5g were placed in a separable flask (IJI),
Next, 445 g of dichloromethane is added and stirred to form a homogeneous solution.
一方、ホモピペラジン（試薬特級 純度９９％以上）
１６．７ｇをジクロロメタン２００ｇに溶解し滴下ロ
ートに入れ、該滴下溶液を前記ＢＭ溶液中に約１詩間を
かけて滴下して室温で反応させる０滴下後、略３０分で
重合ポリマーが析出し始め、更に一昼夜攪拌を続ける。On the other hand, homopiperazine (special reagent grade, purity 99% or more)
Dissolve 16.7 g in 200 g of dichloromethane and put it into a dropping funnel, drop the solution into the BM solution over about 1 hour and react at room temperature. After 0 drops, the polymer precipitates in about 30 minutes. Start stirring all day and night.
次に析出ポリマー中の１．ｐ−クレゾール及びジクロロ
メタンを除去するため、析出ポリマーを細断する。メタ
ノール中で浸漬洗浄後、減圧下でメタノールを除去して
ビスマレイミド樹脂（ＰＢＭ−２）を得る。ＰＢＭ−２
のＧＰＣ分析の結果、及び、各種の溶剤： （アセトン
、メチルエチルケトン、メタノール、インプロパツール
（ＩＰＡ）、）ルエン、クレゾールキシレン、ジクロロ
メタン、トリクレン）に対する溶解の有無を調べて表１
に示した。Next, 1 in the precipitated polymer. The precipitated polymer is shredded to remove p-cresol and dichloromethane. After washing by immersion in methanol, methanol is removed under reduced pressure to obtain bismaleimide resin (PBM-2). PBM-2
Table 1 shows the results of GPC analysis and the presence or absence of dissolution in various solvents (acetone, methyl ethyl ketone, methanol, inpropatol (IPA), luene, cresol xylene, dichloromethane, trichlene).
It was shown to.
［比較例１］
Ｎ、Ｎ−（４，４ジフエルニメタンノービスマレイミ）
’ （ＢＭ純度９６％） ８７．５ｇをセパラブルフラ
スコ（１文）に取り、次にｍ−ｐ−クレゾール２００ｇ
を加えて均一な溶液に攪拌する。[Comparative Example 1] N, N-(4,4 diphernimethane nobismaleimi)
' (BM purity 96%) Take 87.5g into a separable flask (1 sentence), then add 200g of m-p-cresol.
Add and stir to make a homogeneous solution.
一方、ホモピペラジン（試薬特級 純度９９％以上）
２Ｇ、２．をジクロロメタン１３０ｇに溶解し滴下ロー
トに入れ、該滴下溶液を前記ＢＭ溶液中に約１時間をか
けて滴下して１１０℃で反応させる０滴下後更に５時間
、攪拌を続ける。（この際ポリマーの析出は起らなかっ
た。）。On the other hand, homopiperazine (special reagent grade, purity 99% or more)
2G, 2. was dissolved in 130 g of dichloromethane and put into a dropping funnel, and the solution was added dropwise to the BM solution over about 1 hour and reacted at 110° C. After the 0 drop, stirring was continued for another 5 hours. (No polymer precipitation occurred at this time.)
次に、ポリマー履、ｐ−クレゾール溶液をメタノール中
に滴下しポリマーを析出させる。メタノール中で浸漬洗
浄後、減圧下でメタノールを除去してビスマレイミド樹
脂（ＰＢＭ−３）を得る。ＰＢＭ−３のＧＰＣ分析の結
果、及び、各種の溶剤： （アセトン、メチルエチルケ
トン、メタノール、インプロパツール（ＩＰＡ）、
トルエン、クレゾールキシレン、ジクロロメタントリク
レン）に対する溶解の有無を調べて表１に示した。また
、このポリマーから作製した１漠は非常にもろかった。Next, the polymer solution and p-cresol solution are dropped into methanol to precipitate the polymer. After washing by immersion in methanol, methanol is removed under reduced pressure to obtain bismaleimide resin (PBM-3). Results of GPC analysis of PBM-3 and various solvents: (acetone, methyl ethyl ketone, methanol, inproper tool (IPA),
The presence or absence of dissolution in toluene, cresol xylene, dichloromethane trichloromethane) was investigated and the results are shown in Table 1. Also, the samples made from this polymer were very brittle.
［発明の効果］
以上説明したように本発明に係る耐有機溶剤性に優れた
ビスマレイミド樹脂の製造方法によれば、比較的高分子
のビスマレイミド樹脂が得られるので、耐有機溶剤性に
優れ、透過膜材及び充填材としての用途性のある耐有機
溶剤性のビスマレイミド樹脂を提供することができる。[Effects of the Invention] As explained above, according to the method for producing a bismaleimide resin with excellent organic solvent resistance according to the present invention, a bismaleimide resin with a relatively high molecular weight can be obtained, so that the bismaleimide resin with excellent organic solvent resistance can be obtained. , it is possible to provide an organic solvent-resistant bismaleimide resin that is useful as a permeable membrane material and a filler.
Claims (4)
環化合物とをハロゲン系有機溶媒中で、且つ少量のフェ
ノール類の共存下で反応させることを特徴とする耐有機
溶剤性に優れたビスマレイミド系樹脂の製造方法。(1) Production of a bismaleimide resin with excellent organic solvent resistance, which is characterized by reacting a bismaleimide compound and a perhydrodiaza heterocyclic compound in a halogenated organic solvent and in the presence of a small amount of phenols. Method.
ン、２−メチルピペラジン、２，５−ジメチルペラジン
、１，４−ペルヒドロジアゼピン（ホモピペラジン）、
１，３−ジピペラジルプロパンであることを特徴とする
請求項第１項又は第２項記載の耐有機溶剤性ビスマレイ
ミド系樹脂の製造方法。(2) The perhydrodiaza-based heterocyclic compound is piperazine, 2-methylpiperazine, 2,5-dimethylperazine, 1,4-perhydrodiazepine (homopiperazine),
3. The method for producing an organic solvent-resistant bismaleimide resin according to claim 1 or 2, wherein the resin is 1,3-dipiperazylpropane.
て０．５乃至２５重量％の範囲で共存さることを特徴と
する請求第１項記載の耐有機溶剤性に優れたビスマレイ
ミド系樹脂の製造方法。(3) The method for producing a bismaleimide resin having excellent organic solvent resistance according to claim 1, characterized in that the phenol is present in an amount of 0.5 to 25% by weight based on the bismaleimide compound. .
、ｐ−クレゾール、ｍ−イソプロピルフェノール、ｐ−
イソプロピルフェノールハイドロキノン、レゾルシン、
カテコールであることを特徴とする請求項第１項記載の
耐有機溶剤性ビスマレイミド樹脂の製造方法。(4) The phenols are phenol, m-cresol, p-cresol, m-isopropylphenol, p-
Isopropylphenol hydroquinone, resorcinol,
2. The method for producing an organic solvent-resistant bismaleimide resin according to claim 1, wherein catechol is used.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63238448A JPH0286625A (en) | 1988-09-22 | 1988-09-22 | Manufacture of bismaleimide resin excellent in resistance to organic solvent |
| CA000608974A CA1337621C (en) | 1988-08-23 | 1989-08-22 | Membrane filter material having excellent organic solvent resistance, method for formation of membrane filter and process for preparation of bismaleimide polymer to be used formembrane filter |
| US07/396,976 US4983717A (en) | 1988-08-23 | 1989-08-22 | Membrane filter material having excellent organic solvent resistance, method for formation of membrane filter and process for preparation of bismaleimide polymer to be used for membrane filter |
| DE68922802T DE68922802T2 (en) | 1988-08-23 | 1989-08-23 | Membrane filter material with excellent resistance to organic solvents, process for producing the membrane filter and process for producing bismaleimide polymer for use as a membrane filter. |
| EP89308516A EP0356208B1 (en) | 1988-08-23 | 1989-08-23 | Membrane filter material having excellent organic solvent resistance, method for formation of membrane filter and process for preparation of bismaleimide polymer to be used for membrane filter |
| AT89308516T ATE122922T1 (en) | 1988-08-23 | 1989-08-23 | MEMBRANE FILTER MATERIAL WITH EXCELLENT RESISTANCE TO ORGANIC SOLVENTS, METHOD FOR PRODUCING THE MEMBRANE FILTER AND METHOD FOR PRODUCING BISMALEIMIDE POLYMER FOR USE AS A MEMBRANE FILTER. |
| KR1019890011992A KR910009150B1 (en) | 1988-08-23 | 1989-08-23 | Membrane filter material and its making method and process for preparation of polybismaleimide |
| US07/607,283 US5035802A (en) | 1988-08-23 | 1990-10-31 | Membrane filter material having excellent organic solvent resistance, method for formation of membrane filter and process for preparation of bismaleimide polymer to be used for membrane filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63238448A JPH0286625A (en) | 1988-09-22 | 1988-09-22 | Manufacture of bismaleimide resin excellent in resistance to organic solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0286625A true JPH0286625A (en) | 1990-03-27 |
Family
ID=17030371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63238448A Pending JPH0286625A (en) | 1988-08-23 | 1988-09-22 | Manufacture of bismaleimide resin excellent in resistance to organic solvent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0286625A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011006649A (en) * | 2009-06-29 | 2011-01-13 | Sumitomo Bakelite Co Ltd | Resin composition for circuit board, prepreg, and laminated board |
| JP2011084711A (en) * | 2009-09-15 | 2011-04-28 | Sumitomo Bakelite Co Ltd | Resin composition for circuit board, prepreg, laminate, printed wiring board, and semiconductor device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5086597A (en) * | 1973-11-29 | 1975-07-11 | ||
| JPS50142700A (en) * | 1974-03-20 | 1975-11-17 |
-
1988
- 1988-09-22 JP JP63238448A patent/JPH0286625A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5086597A (en) * | 1973-11-29 | 1975-07-11 | ||
| JPS50142700A (en) * | 1974-03-20 | 1975-11-17 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011006649A (en) * | 2009-06-29 | 2011-01-13 | Sumitomo Bakelite Co Ltd | Resin composition for circuit board, prepreg, and laminated board |
| JP2011084711A (en) * | 2009-09-15 | 2011-04-28 | Sumitomo Bakelite Co Ltd | Resin composition for circuit board, prepreg, laminate, printed wiring board, and semiconductor device |
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