JPH03285914A - Copolymer containing acrylamide group and production thereof - Google Patents
Copolymer containing acrylamide group and production thereofInfo
- Publication number
- JPH03285914A JPH03285914A JP8702290A JP8702290A JPH03285914A JP H03285914 A JPH03285914 A JP H03285914A JP 8702290 A JP8702290 A JP 8702290A JP 8702290 A JP8702290 A JP 8702290A JP H03285914 A JPH03285914 A JP H03285914A
- Authority
- JP
- Japan
- Prior art keywords
- component
- cyclic ether
- formula
- acrylamide group
- copolymer
- 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229920001577 copolymer Polymers 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims abstract description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 4
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims abstract description 4
- CZLMRJZAHXYRIX-UHFFFAOYSA-N 1,3-dioxepane Chemical compound C1CCOCOC1 CZLMRJZAHXYRIX-UHFFFAOYSA-N 0.000 claims abstract 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011968 lewis acid catalyst Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 239000003377 acid catalyst Substances 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 2
- 229920000570 polyether Polymers 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- -1 cyclic ether compound Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 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 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- RMWQBWIPOMZVKK-UHFFFAOYSA-N n-[(4-hydroxy-3,5-dimethylphenyl)methyl]prop-2-enamide Chemical compound CC1=CC(CNC(=O)C=C)=CC(C)=C1O RMWQBWIPOMZVKK-UHFFFAOYSA-N 0.000 description 1
- OHBCEHHJPNBVME-UHFFFAOYSA-N n-[[3,5-dimethyl-4-(oxiran-2-ylmethoxy)phenyl]methyl]prop-2-enamide Chemical compound CC1=CC(CNC(=O)C=C)=CC(C)=C1OCC1OC1 OHBCEHHJPNBVME-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規なアクリルアミド基含有共重合体並びに
その製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel acrylamide group-containing copolymer and a method for producing the same.
環状エーテルを開環重合させて得られるポリエーテル樹
脂は、可撓性、伸び、親水性等に優れ、各種接着剤・塗
料等の成分、帯電防止剤、吸水性材料等に用いられる他
、ポリエステル、ポリウレタン等各種ポリマーの原料と
して広く利用されている。Polyether resin obtained by ring-opening polymerization of cyclic ether has excellent flexibility, elongation, and hydrophilicity, and is used as a component of various adhesives and paints, antistatic agents, water-absorbing materials, etc. It is widely used as a raw material for various polymers such as polyurethane.
しかし１分子内に官能基を持たないポリエーテルはその
使用に限界があり、官能基の導入による機能化が試みら
れている。However, there are limits to the use of polyethers that do not have functional groups in one molecule, and attempts have been made to functionalize them by introducing functional groups.
一方、先に本発明者らは分子内にアクリルアミド基を有
する新規な環状エーテルを見いだしく特開昭６０−１３
０５８０号）、エーテル部の開環重合を試みた（特開昭
６１−１６１２４８、特開昭６１−１６２５１９号）、
シかし、ここで得た重合体は分子量の比較的低いオリゴ
マーで、アクリルアミド基を硬化させて得られて硬化物
は低い伸びしか示さなかった。On the other hand, the present inventors previously discovered a novel cyclic ether having an acrylamide group in the molecule, and published JP-A-60-13.
0580), ring-opening polymerization of the ether moiety was attempted (JP-A-61-161248, JP-A-61-162519),
However, the polymer obtained here was an oligomer with a relatively low molecular weight, and the cured product obtained by curing the acrylamide group showed only low elongation.
本発明は、ポリエーテル樹脂中にアクリルアミド基を有
する環状エーテルを共重合し、ポリエーテルの優れた特
性をそのまま残しながら、機能化をはかるものである。The present invention copolymerizes a cyclic ether having an acrylamide group in a polyether resin, and functionalizes the resin while preserving the excellent properties of the polyether.
即ち、本発明の第１は、成分（Ａ）環員数３〜８の環状
エーテルと、成分（Ｂ）アクリルアミド基を含有する環
状エーテルとからなるアクリルアミド基含有共重合体を
、
本発明の第２は、成分（Ａ）環員数３〜８の環状エーテ
ルと、成分（Ｂ）アクリルアミド基を含有する環状エー
テルとを共重合させることを特徴とするアクリルアミド
基含有共重合体の製造方法を、
それぞれ内容とするものである。That is, the first aspect of the present invention is to prepare an acrylamide group-containing copolymer consisting of component (A) a cyclic ether having 3 to 8 ring members and component (B) a cyclic ether containing an acrylamide group. describes a method for producing an acrylamide group-containing copolymer, which comprises copolymerizing component (A) a cyclic ether having 3 to 8 ring members and component (B) a cyclic ether containing an acrylamide group. That is.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
本発明で用いる成分（Ｂ）であるアクリルアミド基を有
する環状エーテルは、同一分子内にアクリルアミド基及
びエポキシ基を含有することを特徴とする。アクリルア
ミド基の代わりにメタアクリルアミド基であっても、何
ら差し支えない、このような化合物は特に構造的に限定
はされないが、一般式（１）で表わされる化合物が好適
である。The cyclic ether having an acrylamide group, which is component (B) used in the present invention, is characterized by containing an acrylamide group and an epoxy group in the same molecule. There is no problem even if a methacrylamide group is used instead of an acrylamide group.Such a compound is not particularly limited structurally, but a compound represented by general formula (1) is preferred.
（式中、Ｒは水素原子又はメチル基、Ａｒは炭素数６〜
２０の２価の芳香族炭化水素基、ｎは１〜４の整数を示
す、）
このような化合物は、例えば特開昭６０−１３０５８０
号に記載されたような方法で製造することができる。即
ち、フェノール性水酸基を少なくとも１個以上有する芳
香族炭化水素とＮ−メチロールアクリルアミド又はＮ−
メチロールメタアクリルアミドを酸性触媒により縮合さ
せた後、水酸基をエピハロヒドリンによってグリシジル
化すると目的の化合物が得られる０例えば、出発物質と
して２．６−キシレノールとＮ−メチロールアクリルア
ミドを用いた場合には、下記構造式（ＩＩ）で表わされ
る化合物を得ることができる。(In the formula, R is a hydrogen atom or a methyl group, and Ar has 6 to 6 carbon atoms.
20 divalent aromatic hydrocarbon groups, n is an integer of 1 to 4) Such compounds are described, for example, in JP-A-60-130580.
It can be manufactured by the method described in No. That is, an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylolacrylamide or N-
After condensing methylolmethacrylamide with an acidic catalyst, the hydroxyl group is glycidylated with epihalohydrin to obtain the desired compound. For example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, the following structure A compound represented by formula (II) can be obtained.
また、出発物質としてオルトクレゾールとＮ−メチロー
ルアクリルアミドを用いた場合には、下記構造式（ＩＩ
Ｉ）
で表わされる化合物を得ることができる。これらは単独
又は２種以上組み合わせて用いられる。In addition, when orthocresol and N-methylolacrylamide are used as starting materials, the following structural formula (II
A compound represented by I) can be obtained. These may be used alone or in combination of two or more.
このようなアクリルアミド基を持つ環状エーテル化合物
は、エーテル部を開環重合させることによりアクリルア
ミド基を側鎖に持つ重合体とすることができる。しかし
乍ら、このものの単独重合では充分に高分子量のものを
得ることは困難である。しかし、驚くべきことに、本発
明の成分（Ａ）である環員数３〜８の環状エーテルとの
共重合を行なうと、実用上充分な高分子量のポリマーが
得られる。Such a cyclic ether compound having an acrylamide group can be made into a polymer having an acrylamide group in a side chain by subjecting the ether moiety to ring-opening polymerization. However, it is difficult to obtain a material with a sufficiently high molecular weight by homopolymerization of this material. However, surprisingly, when copolymerization is carried out with a cyclic ether having 3 to 8 ring members, which is component (A) of the present invention, a polymer having a sufficiently high molecular weight for practical use can be obtained.
共重合に用いられる成分（Ａ）は環員数が３〜８の環状
エーテルであれば特に制限がないが、例えばエチレンオ
キシド、プロピレンオキシド、オキセタン、テトラヒド
ロフラン、スチレンオキシド等；エピクロルヒドリン、
ｎ−ブチルグリシジルエーテル、フェニルグリシジルエ
ーテル等のグリシジルエーテル類ｉ１．３−ジオキソラ
ン、１゜３−ジオキセバン、トリオキサン等のホルマー
ル類が好適に使用できる。これらは単独又は２種以上組
み合わせて用いられる。Component (A) used in the copolymerization is not particularly limited as long as it is a cyclic ether having 3 to 8 ring members, but examples include ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, styrene oxide, etc.; epichlorohydrin,
Glycidyl ethers such as n-butylglycidyl ether and phenylglycidyl ether; formals such as 1.3-dioxolane, 1°3-dioxebane and trioxane can be suitably used. These may be used alone or in combination of two or more.
共重合方法は特に制限されず、硫酸、リン酸、過塩素酸
のようなプロトン酸、又は三フフ化ホウ素、塩化アルミ
ニウム、四塩化チタン、四塩化スズのようなルイス酸触
媒を用いるカチオン重合法；ナトリウムのようなアルカ
リ金属、又はエチルリチウム、ブチルリチウムのような
アルカリ金属アルキル化物触媒を用いるアニオン重合法
；四塩化チタン／トリエチルアルミニウム、三塩化チタ
ン／トリエチルアルミニウムのような遷移金属アルキル
化物触媒を用いる配位重合法等を採用することができる
。The copolymerization method is not particularly limited, and includes cationic polymerization using a protonic acid such as sulfuric acid, phosphoric acid, or perchloric acid, or a Lewis acid catalyst such as boron trifluoride, aluminum chloride, titanium tetrachloride, or tin tetrachloride. Anionic polymerization using an alkali metal catalyst such as sodium or an alkali metal alkyl catalyst such as ethyllithium or butyllithium; Transition metal alkyl catalyst such as titanium tetrachloride/triethylaluminum, titanium trichloride/triethylaluminum Coordination polymerization methods and the like can be employed.
真空あるいは不活性ガス中で、不活性溶剤の存在下又は
非存在下に（Ａ）、（Ｂ）青成分を仕込み、触媒を作用
させて共重合を行なう０反応温度、反応時間は反応速度
を考慮して任意に設定できるが、一般に重合は速やかに
進行する０重合終了後、触媒を失活させるか洗浄するな
どによって除き、溶剤を使用した場合にはこれを留去し
て目的の共重合体を取り出す。In vacuum or inert gas, (A) and (B) blue components are charged in the presence or absence of an inert solvent, and copolymerization is carried out by activating a catalyst.The reaction temperature and reaction time determine the reaction rate. This can be set arbitrarily, but in general, polymerization proceeds quickly. After polymerization is complete, the catalyst is removed by deactivating or washing, and if a solvent is used, it is distilled off to produce the desired copolymer. Take out the combination.
このようにして得られた共重合体は、ポリエーテル樹脂
本来の可撓性、伸び、親木性等を有しながら、側鎖にア
クリルアミド基を有するので、この反応性を利用して所
望の時期に架橋することができる。The copolymer obtained in this way has the flexibility, elongation, wood-philicity, etc. inherent to polyether resins, but also has an acrylamide group in the side chain, so this reactivity can be used to create the desired properties. Can be cross-linked at certain times.
また、このようにして得られた共重合体は、通常、相溶
化が困難である他の樹脂との間でグラフト化を行ない、
ブレンド／アロイ化することが可能となる。従って、本
発明で得られる共重合体はポリエーテル樹脂そのものの
機能化、特性向上に加え、新しいブレンド用樹脂を提供
するという点からも非常に有用なものである。In addition, the copolymer obtained in this way is usually grafted with other resins that are difficult to make compatible,
Blending/alloying is possible. Therefore, the copolymer obtained by the present invention is extremely useful not only for functionalizing and improving the properties of the polyether resin itself, but also for providing a new resin for blending.
本発明で用いられる共重合体は接着／粘着剤、塗料等に
用いられる他、広く樹脂改質剤として帯電防止効果、吸
水性、強靭性付与等の目的で利用される。The copolymer used in the present invention is used in adhesives/pressure-sensitive adhesives, paints, etc., and is also widely used as a resin modifier for purposes such as antistatic effect, water absorption, and imparting toughness.
以下に、本発明を実施例により更に詳細に説明するが、
本発明はこれら実施例のみに限定されるものではない、
尚、１部」は「重量部」を意味する。The present invention will be explained in more detail by examples below.
The present invention is not limited only to these examples.
Note that "1 part" means "part by weight".
参考例１ニアクリルアミド基を有する環状エーテル化合
物の合成
４−アクリルアミドメチル−２，６−シメチルフエノー
ル１０２．６部、エピクロルヒドリン１８１部及びベン
ジルトリエチルアンモニウムクロリド２．２７部の混合
物を１００℃で３０分間攪拌した。この反応混合物を５
０℃に冷却し、５規定水酸化ナトリウム１４７部を攪拌
下１０分で滴下し、その後４５〜５０℃で１時間攪拌し
た。Reference Example 1 Synthesis of a cyclic ether compound having a niacrylamide group A mixture of 102.6 parts of 4-acrylamidomethyl-2,6-dimethylphenol, 181 parts of epichlorohydrin and 2.27 parts of benzyltriethylammonium chloride was heated at 100°C for 30 minutes. Stirred. This reaction mixture was
The mixture was cooled to 0°C, and 147 parts of 5N sodium hydroxide was added dropwise over 10 minutes with stirring, followed by stirring at 45 to 50°C for 1 hour.
これを室温まで冷却し、メチルイソブチルケトン１２０
部及び水５００部を加えて分液した。有機層を３００部
の水で３回水洗し、無水硫酸ナトリウムで脱水した後溶
剤を減圧留去してＮ−（４−（２，３−エポキシプロポ
キシ）−３，５−ジメチルフェニルメチル）アクリルア
ミドを得た。This was cooled to room temperature, and methyl isobutyl ketone 120
1 part and 500 parts of water were added to separate the liquid. The organic layer was washed three times with 300 parts of water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylmethyl)acrylamide. I got it.
ＪＩＳ Ｋ ７２３６の方法で測定したエポキシ当量は
２７１、融点は９０〜９２℃であった。The epoxy equivalent measured by the method of JIS K 7236 was 271, and the melting point was 90 to 92°C.
実施例１
プロピレンオキシド１００部、参考例１で合成したアク
リルアミド基を有する環状エーテル１０部、及び三フッ
化ホウ素モノエチルアミン０．１部を還流冷却器をつけ
たフラスコ中に入れ、室温で２時間攪拌した。得られた
重合体は室温で液状であり、赤外吸収スペクトルを測定
したところ、９１０ｃｍ−’付近のエポキシ基に起因す
る吸収が消失しているのを認めた。また３３００Ｃ１１
−’付近にアミド基に起因する吸収があり、アクリルア
ミド基が共重合により導入されていることを確認した。Example 1 100 parts of propylene oxide, 10 parts of the cyclic ether having an acrylamide group synthesized in Reference Example 1, and 0.1 part of boron trifluoride monoethylamine were placed in a flask equipped with a reflux condenser, and the mixture was heated at room temperature for 2 hours. Stirred. The obtained polymer was liquid at room temperature, and when its infrared absorption spectrum was measured, it was found that the absorption caused by the epoxy group around 910 cm-' had disappeared. Also 3300C11
There was an absorption caused by the amide group near -', and it was confirmed that the acrylamide group was introduced by copolymerization.
Claims (1)
Ｂ）アクリルアミド基を含有する環状エーテルとからな
るアクリルアミド基含有共重合体。 ２、成分（Ａ）がエチレンオキシド、プロピレンオキシ
ド、オキセタン、テトラヒドロフラン、スチレンオキシ
ドから選ばれる少なくとも１種の環状エーテルである請
求項１記載の共重合体。 ３、成分（Ａ）がエピクロルヒドリン、ｎ−ブチルグリ
シジルエーテル、フェニルグリシジルエーテルから選ば
れる少なくとも１種の環状エーテルである請求項１記載
の共重合体。 ４、成分（Ａ）が１，３−ジオキソラン、１，３−ジオ
キセパン、トリオキサンから選ばれる少なくとも１種の
環状エーテルである請求項１記載の共重合体。 ５、成分（Ｂ）が下記一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは水素原子又はメチル基、Ａｒは炭素数６〜
２０の２価の芳香族炭化水素基、ｎは１〜４の整数を示
す。）で表わされる化合物である請求項１記載の共重合
体。 ６、成分（Ｂ）が下記構造式（II） ▲数式、化学式、表等があります▼（II） で表わされる化合物である請求項５記載の共重合体。 ７、成分（Ａ）環員数３〜８の環状エーテルと、成分（
Ｂ）アクリルアミド基を含有する環状エーテルとを共重
合させることを特徴とするアクリルアミド基含有共重合
体の製造方法。 ８、成分（Ａ）がエチレンオキシド、プロピレンオキシ
ド、オキセタン、テトラヒドロフラン、スチレンオキシ
ドから選ばれる少なくとも１種の環状エーテルである請
求項７記載の製造方法。 ９、成分（Ａ）がエピクロルヒドリン、ｎ−ブチルグリ
シジルエーテル、フェニルグリシジルエーテルから選ば
れる少なくとも１種の環状エーテルである請求項７記載
の製造方法。 １０、成分（Ａ）が１，３−ジオキソラン、１，３−ジ
オキセパン、トリオキサンから選ばれる少なくとも１種
の環状エーテルである請求項７記載の製造方法。 １１、成分（Ｂ）が下記一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは水素原子又はメチル基、Ａｒは炭素数６〜
２０の２価の芳香族炭化水素基、ｎは１〜４の整数を示
す。）で表わされる化合物である請求項７記載の製造方
法。 １２、成分（Ｂ）が下記構造式（II） ▲数式、化学式、表等があります▼（II） で表わされる化合物である請求項１１記載の製造方法。 １３、共重合をプロトン酸又はルイス酸触媒の下で行な
う請求項７乃至１２の各項記載の製造方法。 １４、共重合をアルカリ金属又はアルカリ金属アルキル
化物触媒の下で行なう請求項７乃至１２の各項記載の製
造方法。 １５、共重合を遷移金属アルキル化物触媒の下で行なう
請求項７乃至１２の各項記載の製造方法。[Claims] 1. Component (A) a cyclic ether having 3 to 8 ring members, and component (
B) An acrylamide group-containing copolymer consisting of a cyclic ether containing an acrylamide group. 2. The copolymer according to claim 1, wherein component (A) is at least one cyclic ether selected from ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, and styrene oxide. 3. The copolymer according to claim 1, wherein component (A) is at least one cyclic ether selected from epichlorohydrin, n-butyl glycidyl ether, and phenyl glycidyl ether. 4. The copolymer according to claim 1, wherein component (A) is at least one cyclic ether selected from 1,3-dioxolane, 1,3-dioxepane, and trioxane. 5. Component (B) has the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R is a hydrogen atom or a methyl group, Ar is a carbon number of 6 to
20 divalent aromatic hydrocarbon groups, n represents an integer of 1-4. ) The copolymer according to claim 1, which is a compound represented by: 6. The copolymer according to claim 5, wherein the component (B) is a compound represented by the following structural formula (II) ▲A mathematical formula, a chemical formula, a table, etc. ▼(II). 7. Component (A) cyclic ether having 3 to 8 ring members and component (
B) A method for producing an acrylamide group-containing copolymer, which comprises copolymerizing an acrylamide group-containing cyclic ether. 8. The production method according to claim 7, wherein component (A) is at least one cyclic ether selected from ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, and styrene oxide. 9. The manufacturing method according to claim 7, wherein component (A) is at least one cyclic ether selected from epichlorohydrin, n-butylglycidyl ether, and phenylglycidyl ether. 10. The manufacturing method according to claim 7, wherein component (A) is at least one cyclic ether selected from 1,3-dioxolane, 1,3-dioxepane, and trioxane. 11. Component (B) has the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R is a hydrogen atom or a methyl group, Ar is a carbon number of 6 to
20 divalent aromatic hydrocarbon groups, n represents an integer of 1-4. ) The manufacturing method according to claim 7, wherein the compound is a compound represented by: 12. The manufacturing method according to claim 11, wherein component (B) is a compound represented by the following structural formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II). 13. The production method according to each of claims 7 to 12, wherein the copolymerization is carried out under a protonic acid or Lewis acid catalyst. 14. The production method according to each of claims 7 to 12, wherein the copolymerization is carried out under an alkali metal or alkali metal alkylated catalyst. 15. The production method according to any one of claims 7 to 12, wherein the copolymerization is carried out under a transition metal alkylated catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8702290A JPH03285914A (en) | 1990-03-30 | 1990-03-30 | Copolymer containing acrylamide group and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8702290A JPH03285914A (en) | 1990-03-30 | 1990-03-30 | Copolymer containing acrylamide group and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03285914A true JPH03285914A (en) | 1991-12-17 |
Family
ID=13903336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8702290A Pending JPH03285914A (en) | 1990-03-30 | 1990-03-30 | Copolymer containing acrylamide group and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03285914A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2693731A1 (en) * | 1992-07-15 | 1994-01-21 | Centre Nat Rech Scient | Oxirane and dioxolane copolymers, their preparation process and ionically conductive materials containing them. |
-
1990
- 1990-03-30 JP JP8702290A patent/JPH03285914A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2693731A1 (en) * | 1992-07-15 | 1994-01-21 | Centre Nat Rech Scient | Oxirane and dioxolane copolymers, their preparation process and ionically conductive materials containing them. |
| WO1994002534A1 (en) * | 1992-07-15 | 1994-02-03 | Centre National De La Recherche Scientifique (Cnrs) | Oxirane and dioxolane copolymers, process for their preparation and ionic conduction materials containing same |
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