JPS62209120A - N-phenylmaleimide block copolymer - Google Patents
N-phenylmaleimide block copolymerInfo
- Publication number
- JPS62209120A JPS62209120A JP5046486A JP5046486A JPS62209120A JP S62209120 A JPS62209120 A JP S62209120A JP 5046486 A JP5046486 A JP 5046486A JP 5046486 A JP5046486 A JP 5046486A JP S62209120 A JPS62209120 A JP S62209120A
- Authority
- JP
- Japan
- Prior art keywords
- phenylmaleimide
- block copolymer
- formula
- copolymer
- polyethylene glycol
- 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
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229920001400 block copolymer Polymers 0.000 title claims description 16
- 239000000126 substance Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 229920003002 synthetic resin Polymers 0.000 abstract description 2
- 239000000057 synthetic resin Substances 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000001103 continuous-wave nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- -1 polyoxyethylene part Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規なＮ−フェニルマレイミドブロック共重合
体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel N-phenylmaleimide block copolymer.
Ｎ−フェニルマレイミドを共重合させると熱可塑性樹脂
の耐熱温度が向上することから、近年この単量体は注目
を集めている。Copolymerization of N-phenylmaleimide improves the temperature resistance of thermoplastic resins, so this monomer has attracted attention in recent years.
アニオン重合によるＮ−フェニルマレイミドの単独重合
体については既に報告されている〔萩原う、マクロモレ
キュラーレ・ヒエミー−ラピッド・コミュニケーション
Ｍａｋｒｏｍｏｌ。Homopolymers of N-phenylmaleimide produced by anionic polymerization have already been reported [U. Hagiwara, Macromolecules Rapid Communication Makromol.
Ｃｈｅｍ−、Ｒａｐｔｄ Ｃｏｍｍｕｎ、６１６９
（Ｉ９８５）、山田ら、高分子化学紐 １４４（Ｉ９７
２））７５ｆ、Ｎ−フェニルマレイミドフロック共重合
体は文献未記載である。Chem-, Raptd Commun, 6169
(I985), Yamada et al., Polymer Chemical String 144 (I97
2)) 75f, N-phenylmaleimide floc copolymer has not been described in any literature.
本発明は新規なＮ−フェニルマレイミドブロック共重合
体を提供することを目的とする。An object of the present invention is to provide a novel N-phenylmaleimide block copolymer.
イミドブロック共重合体である。It is an imide block copolymer.
本発明のブロック共重合体は一般式（ｎ）のポリエチレ
ングリコールにミ蒙式（ＩＩＩ）のＮ−フェニルマレイ
ミドをアニオン重合することＫよって得られる。The block copolymer of the present invention can be obtained by anionically polymerizing N-phenylmaleimide of formula (III) to polyethylene glycol of general formula (n).
ＨＯ（Ｃ２Ｈ４０）ＢＨ（ＩＩ ）
ｆ−１ｂち、一般式（ＩＩ）のポリエチレングリコール
に、金属ナトリウムなどのアルカリ金属、ナトリウムメ
トキシド、リチウム−ｔ−ブトキシド、カリウム−ｔ−
ブトキシドなどのアルカリ金属アルコラード、ｎ−ブチ
ルリチウムなどの金属アルキル、エチルマグネシウムプ
ロミドなどのグリニヤール試薬等のアルコキシ化剤を加
えてアルコラードに変え、これに乾燥したＮ−フェニル
マレイミドを重合させると本発明のブロック共重合体が
得られる。HO(C2H40)BH(II) f-1b, polyethylene glycol of general formula (II), alkali metal such as sodium metal, sodium methoxide, lithium-t-butoxide, potassium-t-
The present invention can be achieved by adding an alkoxylating agent such as an alkali metal alcoholade such as butoxide, a metal alkyl such as n-butyllithium, or a Grignard reagent such as ethylmagnesium bromide to form an alcoholade, and polymerizing dried N-phenylmaleimide thereto. A block copolymer is obtained.
ポリエチレングリコールに対するアルコキシ化剤の使用
量は、ヒドロキシル基に対して当量ないし１０倍当量、
好ましくは当量ないし３倍当量である。この範囲外では
未反応のポリエチレングリコールあるいは副生ずるＮ−
フェニルマレイミド単独重合体が多くなり、目的とする
ブロック共重合体の収率が低下する。The amount of alkoxylating agent used for polyethylene glycol is equivalent to 10 times equivalent to hydroxyl group,
Preferably it is equivalent to 3 times equivalent. Outside this range, unreacted polyethylene glycol or by-produced N-
The amount of phenylmaleimide homopolymer increases, and the yield of the target block copolymer decreases.
また重合の際に、テトラヒドロフラン、トルエン、／ク
ロヘキサン、ジメトキシエタン等の不活性溶媒を用いて
もよい。Further, during polymerization, an inert solvent such as tetrahydrofuran, toluene, chlorohexane, dimethoxyethane, etc. may be used.
重合温度は通常−８０℃ないし１５０℃、好ましくは一
２０℃ないし５０℃である。The polymerization temperature is usually -80°C to 150°C, preferably -20°C to 50°C.
重合反応終了後、未反応のＮ−フェニルマレイミド、ポ
リエチレングリコールおよび副生したＮ−フェニルマレ
イミド単独重合体は、反応混合物から溶媒精製によって
除去される。After the polymerization reaction is completed, unreacted N-phenylmaleimide, polyethylene glycol, and by-produced N-phenylmaleimide homopolymer are removed from the reaction mixture by solvent purification.
本発明のブロック共重合体は新規な重合体であり、耐熱
性に優れたポリ−Ｎ−フェニルマレイミド部分と親水性
に優れたポリオキシエチレン部分をもっているため、合
成樹脂に耐熱性や親水性を付与する改質剤として、また
高分子界面活性剤としての用途が期待される。The block copolymer of the present invention is a new polymer and has a poly-N-phenylmaleimide part with excellent heat resistance and a polyoxyethylene part with excellent hydrophilicity, so it imparts heat resistance and hydrophilicity to synthetic resins. It is expected to be used as a modifier and as a polymeric surfactant.
本発明を実施例により説明する。 The present invention will be explained by examples.
実施例 １
平均分子量９３０のポリエチレングリコール（ＰＥＧ−
１０００、一般式（ＩＩ）においてａｍ２１）ＬＯＰ（
０，０１モル）をフラスコにとり、ベンゼン１００ｍ／
を加えて共沸脱水を行った。ついで乾燥ベンゼンを加え
て均一に溶解させ、これに１０％ｎ−ブチルリチウムの
ｎ−ヘキサン溶液ＩＺ８ｒ（０，０２モル）を加えて均
一溶液となし、溶媒を留去したのち、乾燥テトラヒドロ
フランを加えてＰＥＧ−１０００のりチウムアルコラー
ドの１０％テトラヒドロフラン溶液を得た。Example 1 Polyethylene glycol (PEG-
1000, in general formula (II) am21) LOP(
0.01 mol) in a flask and add benzene 100m/
was added to perform azeotropic dehydration. Next, dry benzene was added and dissolved uniformly, a 10% n-butyllithium n-hexane solution IZ8r (0.02 mol) was added to make a homogeneous solution, the solvent was distilled off, and dry tetrahydrofuran was added. A 10% tetrahydrofuran solution of PEG-1000 adhesive alcoholade was obtained.
このＰＥＧ−１０００のりチウムアルコラードの１０９
６テトラヒドロフラン溶液ｏ、 ｓ ｒ （ｏ、 ｏ
ｓミリモル）、テトラヒドロフラン’ｌＱｍｌおよびＮ
−フェニルマレイミドｔ７３Ｆ（Ｉ０ミリモル）をガラ
ス製のアンプルにとり、０℃で２４時間重合を行ったの
ち、５チ塩酸メタノール溶液ｔｏｅを加えて重合を停止
させた。つぎに、反応混合物を大量のメタノール中に投
入して沈でん物を得、未反応のＰＥＧ−１０００および
Ｎ−フェニルマレイミドを除去した。つぎに沈でん物に
テトラヒドロフラン２０ ｍｌを加えて溶解し、これを
大金のヘンセン中ニ投入してＮ−フェニルマレイミド単
独重合体を沈でんさせて除去し、溶液中のテトラヒドロ
フランを減圧下に留去して白色固体ｏ、９２ｙ （ＰＥ
Ｇ−ｔ Ｏ００とＮ−フェニルマレイミドの合計機に対
する収率５２チ）を得た。This PEG-1000 adhesive 109
6 Tetrahydrofuran solution o, s r (o, o
s mmol), tetrahydrofuran'lQml and N
-Phenylmaleimide t73F (I0 mmol) was placed in a glass ampoule and polymerized at 0° C. for 24 hours, then a methanol solution of 5-thihydrochloric acid was added to stop the polymerization. Next, the reaction mixture was poured into a large amount of methanol to obtain a precipitate, and unreacted PEG-1000 and N-phenylmaleimide were removed. Next, 20 ml of tetrahydrofuran was added to the precipitate to dissolve it, and this was poured into a large Hensen solution to precipitate and remove the N-phenylmaleimide homopolymer, and the tetrahydrofuran in the solution was distilled off under reduced pressure. White solid o, 92y (PE
A total yield of G-t O00 and N-phenylmaleimide of 52 cm was obtained.
得られた生成物のＩＲ吸収スペクトル図を図１に、’Ｈ
−ＮＭＲ吸収スペクトル図を図２に示す。The IR absorption spectrum of the obtained product is shown in Figure 1.
-NMR absorption spectrum diagram is shown in FIG. 2.
この結果から得られた生成物がブロック共重合体である
ことを確認した。また、薄層クロマトグラフィーからも
ブロック共重合体であることを確認した。From this result, it was confirmed that the obtained product was a block copolymer. It was also confirmed by thin layer chromatography that it was a block copolymer.
このブロック共重合体の平均分子量は、ゲルパーミェー
ションクロマトグラフィーの結果から、１８４００であ
った。The average molecular weight of this block copolymer was 18,400 based on the results of gel permeation chromatography.
実施例 ２〜５
実施例１と同様にして表１に示す条件で重合を行ない、
同表に示すブロック共重合体を得た。Examples 2 to 5 Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1,
A block copolymer shown in the same table was obtained.
なお、実施例５は溶媒としてテトラヒドロフランの代り
にジメトキシエタンを用いた。Note that in Example 5, dimethoxyethane was used instead of tetrahydrofuran as the solvent.
実施例 ６〜１２
ポリエチレングリコールとして平均分子量１４６００Ｐ
ＥＧ−１５４０（一般式（Ｉｔ）においてａ＝３３ ）
を用い、実施例１と同様にして表１に示す条件で重合を
行ない、同表に示すブロック共重合体を得た。Examples 6 to 12 Average molecular weight 14600P as polyethylene glycol
EG-1540 (a=33 in general formula (It))
Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1 to obtain the block copolymers shown in Table 1.
図１は実施例１で得たＮ−フェニルマレイミドブロック
共重合体のＩＲ吸収スペクトル図（ｎｅａｔ）であり、
図２は同じブロック共重合体の’Ｈ−ＮＭＲ吸収スペク
トル図（Ｒｅｆｅｒｅｎｃｅ：ＴＭＳ＋ Ｓｏ １ｖ
ｅｎｔ ：ＣＤＣ４ｇ ）である。FIG. 1 is an IR absorption spectrum diagram (neat) of the N-phenylmaleimide block copolymer obtained in Example 1,
Figure 2 shows the 'H-NMR absorption spectrum of the same block copolymer (Reference: TMS+ So 1v
ent: CDC4g).
Claims (1)
ブロック共重合体。 ▲数式、化学式、表等があります▼（ I ） （ただし、ａは２ないし５００、ｂ≧０、Ｃ≧０でｂ＋
ｃは２ないし５００である。）[Claims] 1. N-phenylmaleimide block copolymer represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, a is 2 to 500, b≧0, C≧0 and b+
c is 2 to 500. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5046486A JPS62209120A (en) | 1986-03-10 | 1986-03-10 | N-phenylmaleimide block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5046486A JPS62209120A (en) | 1986-03-10 | 1986-03-10 | N-phenylmaleimide block copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62209120A true JPS62209120A (en) | 1987-09-14 |
Family
ID=12859599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5046486A Pending JPS62209120A (en) | 1986-03-10 | 1986-03-10 | N-phenylmaleimide block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62209120A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02199128A (en) * | 1989-01-27 | 1990-08-07 | Sanyo Chem Ind Ltd | Modifier for resin |
| JPH02199127A (en) * | 1989-01-27 | 1990-08-07 | Sanyo Chem Ind Ltd | Modifier for resin |
| JPH02199129A (en) * | 1989-01-27 | 1990-08-07 | Sanyo Chem Ind Ltd | Modifier for resin |
| JPH03294333A (en) * | 1990-04-11 | 1991-12-25 | Sanyo Chem Ind Ltd | Resin modifier |
-
1986
- 1986-03-10 JP JP5046486A patent/JPS62209120A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02199128A (en) * | 1989-01-27 | 1990-08-07 | Sanyo Chem Ind Ltd | Modifier for resin |
| JPH02199127A (en) * | 1989-01-27 | 1990-08-07 | Sanyo Chem Ind Ltd | Modifier for resin |
| JPH02199129A (en) * | 1989-01-27 | 1990-08-07 | Sanyo Chem Ind Ltd | Modifier for resin |
| JPH03294333A (en) * | 1990-04-11 | 1991-12-25 | Sanyo Chem Ind Ltd | Resin modifier |
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