JPS6337109A - Novel polymer having glycidyl group and production thereof - Google Patents
Novel polymer having glycidyl group and production thereofInfo
- Publication number
- JPS6337109A JPS6337109A JP18116286A JP18116286A JPS6337109A JP S6337109 A JPS6337109 A JP S6337109A JP 18116286 A JP18116286 A JP 18116286A JP 18116286 A JP18116286 A JP 18116286A JP S6337109 A JPS6337109 A JP S6337109A
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- formula
- formulas
- polymer
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- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 28
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000178 monomer Substances 0.000 claims abstract description 9
- -1 glycidyloxy group Chemical group 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- WORJRXHJTUTINR-UHFFFAOYSA-N 1,4-dioxane;hydron;chloride Chemical compound Cl.C1COCCO1 WORJRXHJTUTINR-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OJVQNVMHJWSOSY-UHFFFAOYSA-N 3-methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(O)=O)(C)C2C(O)=O OJVQNVMHJWSOSY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はグリシジル基を有する新規な重合体及びその製
造方法に関するものである。本発明の重合体は、塗料、
接着剤、ポリマー改質剤として、又その成形体は構造材
料などとして有用である。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel polymer having a glycidyl group and a method for producing the same. The polymer of the present invention can be used in coatings,
It is useful as an adhesive, a polymer modifier, and its molded product as a structural material.
（従来の技術と問題点） エポキシ樹脂は機械的強度、接着性、耐熱性。(Conventional technology and problems) Epoxy resin has mechanical strength, adhesive properties, and heat resistance.
電気的特性などに優れていることから接着、塗料、電気
、土木の分野で広く用いられてきている。用いられるエ
ポキシ樹脂としてはフェノール系が一般的であるが、末
端に数個のエポキシ基しか入らないこと、溶媒として極
性溶媒を必要とすること、などが難点としてあげられる
。Due to its excellent electrical properties, it has been widely used in the fields of adhesives, paints, electricity, and civil engineering. Phenolic resins are commonly used as epoxy resins, but their drawbacks include the fact that only a few epoxy groups can be present at the ends and that a polar solvent is required.
（問題点を解決する丸めの手段と作用効果）本発明者ら
は、優れた耐熱性を有する。エポキシ官能基を吃った反
応性樹脂について鋭意研究を重ねた結果、本発明に到達
した。すなわち本発明は、一般式（１）
％式％
Ｃ式中、Ａｒけグリシジルオキシ基を少なくとも１つ以
上有する０６〜ＯＮの芳香族炭化水素基を表わし、Ｒ１
，Ｒ１は水素原子又はメチル基であり、Ｒｓは水素原子
、Ｃ１〜Ｃ１・の炭化水素基、−ＣＯＯＣＨｍ を−Ｃ
ｏ０ＣＩＨＢ 、−Ｃｏｏ（ＣＴｈ ）ｓ ＣＨｓ ｇ
ハロゲン原子又はシアノ基を示し、ｍは１以上の整数、
ｎけ整数を表わし、ｍとｎの和に対するｎの比率￥ｉ０
〜０．９９ であり、ｍとｎの和は１０〜１００，００
０である）で表わされる、グリシジル基を有する新規重
合体及びその製造方法に関する。(Means for rounding and effects to solve the problem) The present inventors have excellent heat resistance. As a result of extensive research into reactive resins containing epoxy functional groups, we have arrived at the present invention. That is, the present invention provides general formula (1) %Formula%C in the formula, Ar represents an aromatic hydrocarbon group of 06 to ON having at least one glycidyloxy group, and R1
, R1 is a hydrogen atom or a methyl group, Rs is a hydrogen atom, a C1-C1 hydrocarbon group, -COOCHm is a -C
o0CIHB , -Coo(CTh)s CHs g
represents a halogen atom or a cyano group, m is an integer of 1 or more,
Represents an n-digit integer, the ratio of n to the sum of m and n ¥i0
~0.99, and the sum of m and n is 10~100,00
The present invention relates to a novel polymer having a glycidyl group represented by 0) and a method for producing the same.
本発明のグリシジル基を有する新規重合体は、下記一般
式（Ｖ）で表わされるグリシジル基を有する単量体単独
あるいはこれと下記一般式（■）で表わされる他のビニ
ルモノマーとの共重合によって製造される。The novel polymer having a glycidyl group of the present invention can be obtained by copolymerizing a monomer having a glycidyl group represented by the following general formula (V) alone or by copolymerizing this with another vinyl monomer represented by the following general formula (■). Manufactured.
ＣＥｈ ＝ ＣＢ’ Ｒ” （
■）Ｃ式中、Ａｒ、 Ｒ’、 Ｒ”、 Ｒコは前記
に同じ）一般式（■）で表わされる化合物は、例えばフ
エノール性水酸基を少なくとも１つ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あるいはＮ−
メチロールメタクリルアミドあるいＨｌＮ−メチロール
メタクリルアミドまたＨＮ−メチロールメタクリルアミ
ドのアルキルエーテル誘導体Ｃ以下、これらをＮ−メチ
ロールアクリルアミド類という）を酸触媒で縮合させた
後、フェノール性水酸基をグリシジル化することにより
容易に得られる。CEh = CB'R" (
(2) In formula C, Ar, R', R'', R are the same as above) The compound represented by general formula (■) is, for example, an aromatic hydrocarbon having at least one phenolic hydroxyl group, and N- Methyloracrylamide or N-
By condensing methylolmethacrylamide, HlN-methylolmethacrylamide, or alkyl ether derivatives of HN-methylolmethacrylamide (hereinafter referred to as N-methylolmethacrylamides) with an acid catalyst, and then glycidylating the phenolic hydroxyl group. easily obtained.
たと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類を用いた場合、下記構造式
（■）で表わされるグリシジル化合物を得ることができ
る。For example, starting materials include 2,6-xylenol and N-
When methylol acrylamide is used, a glycidyl compound represented by the following structural formula (■) can be obtained.
（式中、Ｂｌは水素原子またはメチル基を示す）また出
発物質として、オルトクレソーＡＩトＮ−メチローＶア
クリルアミド類を用いた場合、下記構造式備）で表わさ
れるグリシジＶ化合物を得ることができる。(In the formula, Bl represents a hydrogen atom or a methyl group.) When ortho-creso AI to N-methylo-V acrylamide is used as a starting material, a glycidi-V compound represented by the following structural formula can be obtained.
Ｉ Ｏ
（式中、Ｒ１は水素原子またはメチル基を示す）上記一
般式（ｖ）、（Ｍ）で表わされる単量体の重合について
検討した結果、単量体（■）単独またはこれと単量体（
■）の溶液中でのラジカル重合により好適に前記一般式
（１）で表わされる共重合体が得られることが判った。I O (wherein R1 represents a hydrogen atom or a methyl group) As a result of studying the polymerization of the monomers represented by the above general formulas (v) and (M), it was found that the monomer (■) alone or together with the monomer Quantity (
It has been found that the copolymer represented by the above general formula (1) can be suitably obtained by radical polymerization in a solution ((2)).
上記の共重合に用いることができる重合体（■）として
は、ビニリデン基を有する任意のものが使用できるが、
例示すれば、エチレン、プロピレン、１−ブテン、イソ
ブチン、スチレン、α−メチルスチレン、０１ ｍ、
ｐ−アルギルスチレン、ブタジェン、イソプレン、塩化
ビニｖ１フッ化ビニル、アクリル酸メチル、メタクリＶ
酸メチル、アクリｖ酸エチＶ、メタクリル酸エチル、ア
クリル酸ｎ−ブチル、アクリロニトリルなどがあげられ
る。As the polymer (■) that can be used in the above copolymerization, any polymer having a vinylidene group can be used, but
Examples include ethylene, propylene, 1-butene, isobutyne, styrene, α-methylstyrene, 01 m,
p-Argylstyrene, butadiene, isoprene, vinyl chloride v1 vinyl fluoride, methyl acrylate, methacrylate V
Examples include methyl acrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, and acrylonitrile.
本発明における重合は、一般に用いられるラジカル開始
剤により開始されるが、例示すればクメンヒドロペルオ
キシド、第三ブチルヒドロペルオキシドのようなべＶオ
キシド系、過酸化ベンシイＶ、過酸化ラウロイルなどの
過酸化物系、或いはアゾビスイソブチロニトリルのよう
なアゾ化合物が用いられる。The polymerization in the present invention is initiated by a commonly used radical initiator, and examples thereof include cumene hydroperoxide, tertiary-butyl hydroperoxide, and other peroxides such as benzyV peroxide and lauroyl peroxide. or an azo compound such as azobisisobutyronitrile.
ラジカル重合で得られた本発明のグリシジル基を有する
新規重合体は、常温で粘稠な液状〜固体状であり、単独
、あるいはアミン系、力Ｖボン酸無水物系などの一般に
エポキシ樹脂硬化剤として用いられる化合物との併用に
よる熱硬化により硬化物を得ることができる。The novel polymer having a glycidyl group of the present invention obtained by radical polymerization is in a viscous liquid to solid state at room temperature, and can be used alone or in general as an epoxy resin curing agent such as an amine type or a V-oxygen acid anhydride type. A cured product can be obtained by thermal curing in combination with a compound used as a compound.
また本発明によって得られた重合体は他のポリマーの反
応性改質剤として用いることが可能である。この用途に
用いる場合、他の七ツマ−あるいはポリマーへの溶解度
が問題となる。そこで、種々の溶媒に対する溶解度を測
定したところ、９〜１０のｅｐ値をもったクロロホルム
、酢酸エチル、アセトンなどの溶媒に可溶であることが
わかった。結果を実施例１６に示した。Furthermore, the polymer obtained according to the present invention can be used as a reactive modifier for other polymers. When used in this application, solubility in other polymers or polymers becomes a problem. Then, when the solubility in various solvents was measured, it was found that it is soluble in solvents such as chloroform, ethyl acetate, and acetone having an ep value of 9 to 10. The results are shown in Example 16.
（実施例）
以下に本発明を実施例により説明するが、本発明はこれ
ら実施例のみに限定されるものではない。(Examples) The present invention will be explained below using Examples, but the present invention is not limited only to these Examples.
実施例１
Ｎｘ 言回９−Ｃ下、２０震ｌのメチルエチルケトンへ
、借拌中、加熱還流下、Ｎ−（４−グリシジｌレオキシ
−５，５−ジメチＶフェニルメチル）アクリルアミド２
６．１ ｆｌ （０，１モル）スチレン１α４ｇ（０，
１モＶ）、アゾビスイソブチロニトリル（ＡよりＮ）
１．６４ ｆ （０，０１モル）のメチルエチルケトン
（１２ｏｆｆ／）溶液を４〜５時間かけて滴下した。滴
下後、Ａ工ＥＮ Ｏ，３３ｆ （２ｍＭ ）のＭＥＫ（
１０ｇｌ）溶液を添加し、１時間加熱還流し、その後、
更にＡよりＮ Ｏ，３３ｆｌ （２ｍＭ ）のｕｙｔＫ
（１ｏｖｔｌ）溶液を添加し、１時間加熱還流した。反
応混合物を冷却後濾過［７、減圧下溶媒を留去した。そ
の後、樹脂ｆｔ’ｓ ｏｏＣで２時間減圧下乾燥した。Example 1 N-(4-Glycidyl-leoxy-5,5-dimethyV-phenylmethyl)acrylamide 2 to 20 l of methyl ethyl ketone under Nx phrase 9-C while stirring and heating under reflux.
6.1 fl (0,1 mol) styrene 1α4g (0,
1 mo V), azobisisobutyronitrile (A to N)
A 1.64 f (0.01 mol) solution of methyl ethyl ketone (12 off/) was added dropwise over 4 to 5 hours. After dropping, MEK(
10gl) solution and heated to reflux for 1 hour, then
Furthermore, NO, 33fl (2mM) of uytK was added from A.
(1 ovtl) solution was added and heated to reflux for 1 hour. The reaction mixture was cooled and filtered [7, and the solvent was distilled off under reduced pressure. Thereafter, it was dried under reduced pressure using resin ft's ooC for 2 hours.
ここで得られた樹脂をアセトン（〜１００！１？）に溶
解し、メタノール（１１りに注ぎ、再沈殿を行ない、メ
タノール層をデカンテーションで除き、更にメタノール
で数回洗浄し、得られた水飴状ａ脂を減圧下、８０°Ｃ
で２時間乾燥し、固体粉末状の樹脂１２．８ｆを得た。The resin obtained here was dissolved in acetone (~100!1?), poured into methanol (11), reprecipitated, the methanol layer was removed by decantation, and further washed several times with methanol. Starch syrup-like fat under reduced pressure at 80°C
The mixture was dried for 2 hours to obtain 12.8f of solid powdery resin.
得られた樹脂の塩酸−ジオキサン法によるエポキシ当量
ば４５９であった、
実施例２
スチレンの代わりに、メタクリル酸メチル１０、１ ｙ
（Ｄ、 １モル）用すた以外は実施例１と同様の操作を
行ない、固体粉末状樹脂を１０．５Ｎ得た。The epoxy equivalent of the obtained resin by the hydrochloric acid-dioxane method was 459. Example 2 Methyl methacrylate was used in place of styrene at 10.1 y.
(D, 1 mol) The same operation as in Example 1 was carried out except for the amount used, and 10.5N of solid powdery resin was obtained.
エポキシ当量はろ９８であった。The epoxy equivalent was 98.
実施例３
スチレンの代わりにアクリル酸フチル１２．８Ｆ（０，
１そル）を用いた以外は実施例１と同様の操作を行ない
、固体粉末状樹脂ＩＱ、１Ｆを得た。Example 3 Phthyl acrylate 12.8F (0,
Solid powdered resins IQ and 1F were obtained by carrying out the same operation as in Example 1, except that 1.1 ml) was used.
エポキシ当量け４１４であった。The epoxy equivalent weight was 414.
実施例４
Ｎ−（４−グリシジルオキシ−３，５−シメ＋ルフェニ
ルメチ７Ｌ／）アクリルアミド２６．１ｇとスチレン１
０．４ｐを用いる代わりに、Ｎ−（ａ−グリシジルオキ
シ−３，５ジメチルフエニルメチル）アクリルアミド５
２．２１ （０，２モＩｖ）用いた以外は実施例１と同
様の操作を行なうことにより固体粉末状樹脂ｘ５．ｏｙ
を得た。エポキシ当」は２９２であった。Example 4 26.1 g of N-(4-glycidyloxy-3,5-cyme+ruphenylmethy 7 L/)acrylamide and 1 styrene
Instead of using 0.4p, N-(a-glycidyloxy-3,5dimethylphenylmethyl)acrylamide 5
2.21 (0.2 mo Iv) was used, but the same operation as in Example 1 was performed to obtain solid powder resin x5. oy
I got it. The epoxy weight was 292.
実施例５〜１０
下表の仕込み比で実施例１と同様の操作により重合を行
ない、それぞれ粉末状の樹脂を得た。Examples 5 to 10 Polymerization was carried out in the same manner as in Example 1 using the charging ratios shown in the table below to obtain powdered resins.
樹脂のエポキシ当量とあわせて表１に示す。Table 1 shows the epoxy equivalent weight of the resin.
表 １
以上の実施例１〜１０で得られたポリマーのＧＰＣによ
る分子量測定を行なった結果、数平均分子量は表２の通
りであった、
表 ２
実施例１１
実施例１で得られた重合体１０ｙ、無水メチルハイミッ
ク酸５．４５ｆ、ベンジルジメチルアミン００７ｇを混
合し、１００″Ｃで１時間１５０″Ｃで２時間硬化させ
た。得られた硬化物の熱変形温度（ＡＳＴＭ−Ｄ−６１
１８）は１０８℃であった。Table 1 As a result of measuring the molecular weight by GPC of the polymers obtained in Examples 1 to 10 above, the number average molecular weights were as shown in Table 2. Table 2 Example 11 Polymer obtained in Example 1 10y, 5.45f of methylhimic anhydride, and 007g of benzyldimethylamine were mixed and cured at 100''C for 1 hour and 150''C for 2 hours. The heat distortion temperature of the obtained cured product (ASTM-D-61
18) was 108°C.
実施例１２〜１５
実施例３．４．５．７で得られた一合体、そのエポキシ
当ｍｔｖ ｏ、ｓ ５ 倍当量の無水メチルハイミック
酸、ベンジルジメチルアミン（重合体に対シてα７ ｗ
ｔ％）を混合し、実施例１１と同様の操作により硬化物
を得て、熱変形温度（ＨＤＴ ）を測定した。結果を表
３に示す。Examples 12-15 The monomer obtained in Example 3.4.5.7, its epoxy mtvo, s 5 times equivalent of methylhimic acid anhydride, benzyldimethylamine (α7 w relative to the polymer)
t%) was mixed, a cured product was obtained by the same operation as in Example 11, and the heat distortion temperature (HDT) was measured. The results are shown in Table 3.
表 ３
実施例１６
実施例１〜１０で得られた重合体０．２９に下記表４の
溶媒１ ｍｌを加え、−嵐夜放置後の溶解性を評価した
。結果を表４に示す。Table 3 Example 16 1 ml of the solvent shown in Table 4 below was added to 0.29 g of the polymers obtained in Examples 1 to 10, and the solubility after being left on a stormy night was evaluated. The results are shown in Table 4.
表 ４
評価二 〇二均−に溶解
△ニ一部溶解し、一部オイル状に分離
×：タール状に分離し、はとんど溶解せず××：粉状の
まま不溶Table 4 Evaluation 2 〇 Two-uniformly dissolved △ Partially dissolved and partially separated into an oily form
Claims (1)
を有する新規重合体。 ▲数式、化学式、表等があります▼（ I ） （式中、Ａｒはグリシジルオキシ基を少なくとも１つ以
上有するＣ＿６〜Ｃ＿２＿０の芳香族炭化水素基を表わ
し、Ｒ＾１、Ｒ＾２は水素原子又はメチル基であり、Ｒ
＾３は水素原子、Ｃ＿１〜Ｃ＿１＿０の炭化水素基、−
ＣＯＯＣＨ＿３、−ＣＯＯＣ＿２Ｈ＿５、−ＣＯＯ（Ｃ
Ｈ＿２）＿３ＣＨ＿３、ハロゲン原子又はシアノ基を示
し、ｍは１以上の整数、ｎは整数を表わし、ｍとｎの和
に対するｎの比率は０〜０．９９であり、ｍとｎの和は
１０〜１００，０００である） （２）グリシジル基を有する重合体が下記一般式（II）
で表わされる特許請求の範囲第１項記載の新規重合体。 ▲数式、化学式、表等があります▼（II） （式中、Ｒ＾１、Ｒ＾２、Ｒ＾３、ｍ、ｎは前記に同じ
、Ｒ＾４、Ｒ＾５は水素原子、Ｃ＿１〜Ｃ＿４のアルキ
ル基、又はＣ＿６〜Ｃ＿１＿０の芳香族基を表わす）（
３）グリシジル基を有する重合体が下記一般式（III）
わされる特許請求の範囲第１項記載の新規重合体。 ▲数式、化学式、表等があります▼（III） （式中、Ｒ＾１、Ｒ＾２、Ｒ＾３、ｍ、ｎは前記に同じ
）（４）グリシジル基を有する重合体が下記一般式（I
V）で表わされる特許請求の範囲第１項記載の新規重合
体。 ▲数式、化学式、表等があります▼（IV） （式中、Ｒ＾１、Ｒ＾２、Ｒ＾３、ｍ、ｎは前記に同じ
）（５）下記一般式（Ｖ） ▲数式、化学式、表等があります▼ （式中、Ａｒはグリシジルオキシ基を少なくとも１つ以
上有するＣ＿４〜Ｃ＿２＿０の芳香族炭化水素基を表わ
し、Ｒ＿１は水素原子又はメチル基を表わす） で表わされる単量体をラジカル重合するこ とを特徴とするグリシジル基を有する新規重合体の製造
方法。 （６）下記一般式（Ｖ）と（VI） ▲数式、化学式、表等があります▼（Ｖ） Ｈ＿２Ｃ＝ＣＲ＾２Ｒ＾２（VI） （式中、Ａｒはグリシジルオキシ基を少なくとも１つ以
上有するＣ＿■〜Ｃ＿２＿０の芳香族炭化水素基を表わ
し、Ｒ＾１、Ｒ＾２は水素原子又はメチル基であり、Ｒ
＾３は水素原子、Ｃ＿１〜Ｃ＿１＿０の炭化水素基、−
ＣＯＯＣＨ＿３、−ＣＯＯＣ＿２Ｈ＿５、−ＣＯＯ（Ｃ
Ｈ＿２）＿３ＣＨ＿３、ハロゲン原子又はシアノ基を表
わす） で表わされる単量体をラジカル共重合する ことを特徴とする一般式（ I ） ▲数式、化学式、表等があります▼ （式中、Ａｒ、Ｒ＾１、Ｒ＾２、Ｒ＾３は前記に同じ、
ｍは１以上の整数、ｎは整数を表わし、ｍとｎの和に対
するｎの比率は０〜０．９９であり、ｍとｎとの和は１
０〜１００，０００である）で表わされる、グリシジル
基を有する新規 重合体の製造方法。[Scope of Claims] (1) A novel polymer having a glycidyl group, represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, Ar represents a C_6 to C_2_0 aromatic hydrocarbon group having at least one glycidyloxy group, and R^1 and R^2 are hydrogen atoms. or a methyl group, R
^3 is a hydrogen atom, C_1 to C_1_0 hydrocarbon groups, -
COOCH_3, -COOC_2H_5, -COO(C
H_2)_3CH_3 represents a halogen atom or a cyano group, m represents an integer of 1 or more, n represents an integer, the ratio of n to the sum of m and n is 0 to 0.99, and the sum of m and n is 10 100,000) (2) The polymer having a glycidyl group has the following general formula (II)
A novel polymer according to claim 1, which is represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R^1, R^2, R^3, m, n are the same as above, R^4, R^5 are hydrogen atoms, C_1 ~ represents an alkyl group of C_4 or an aromatic group of C_6 to C_1_0) (
3) The polymer having a glycidyl group has the following general formula (III)
A novel polymer according to claim 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, R^1, R^2, R^3, m, and n are the same as above) (4) The polymer having a glycidyl group has the following general formula (I
V) The novel polymer according to claim 1, which is represented by V). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R^1, R^2, R^3, m, and n are the same as above) (5) General formula (V) below ▲Mathematical formula, chemical formula , tables, etc. ▼ (In the formula, Ar represents a C_4 to C_2_0 aromatic hydrocarbon group having at least one glycidyloxy group, and R_1 represents a hydrogen atom or a methyl group.) A method for producing a novel polymer having a glycidyl group, which is characterized by undergoing radical polymerization. (6) General formulas (V) and (VI) below ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) H_2C=CR^2R^2(VI) (In the formula, Ar has at least one glycidyloxy group represents an aromatic hydrocarbon group having C_■ to C_2_0, R^1 and R^2 are hydrogen atoms or methyl groups, and R
^3 is a hydrogen atom, C_1 to C_1_0 hydrocarbon groups, -
COOCH_3, -COOC_2H_5, -COO(C
General formula (I) characterized by radical copolymerization of a monomer represented by H_2)_3CH_3 (representing a halogen atom or a cyano group) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar, R ^1, R^2, R^3 are the same as above,
m represents an integer greater than or equal to 1, n represents an integer, the ratio of n to the sum of m and n is 0 to 0.99, and the sum of m and n is 1.
0 to 100,000) and has a glycidyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18116286A JPS6337109A (en) | 1986-07-31 | 1986-07-31 | Novel polymer having glycidyl group and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18116286A JPS6337109A (en) | 1986-07-31 | 1986-07-31 | Novel polymer having glycidyl group and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6337109A true JPS6337109A (en) | 1988-02-17 |
| JPH0577683B2 JPH0577683B2 (en) | 1993-10-27 |
Family
ID=16095970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18116286A Granted JPS6337109A (en) | 1986-07-31 | 1986-07-31 | Novel polymer having glycidyl group and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6337109A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991017192A1 (en) * | 1990-04-28 | 1991-11-14 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Modified polyolefin polymer, production thereof, and resin composition containing the same |
| WO1992009643A1 (en) * | 1990-11-30 | 1992-06-11 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Vinylic polymer and production thereof |
| EP0522163A1 (en) * | 1990-03-28 | 1993-01-13 | MITSUI TOATSU CHEMICALS, Inc. | Modified polyolefin resin composition |
| WO1993007218A1 (en) * | 1990-04-13 | 1993-04-15 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Thermoplastic resin composition and production thereof |
| WO1993007215A1 (en) * | 1991-10-01 | 1993-04-15 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Thermoplastic resin composition and production thereof |
| US5728791A (en) * | 1990-11-30 | 1998-03-17 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Polyvinyl graft-polymers and manufacturing method thereof |
| JP2772870B2 (en) * | 1990-04-28 | 1998-07-09 | 鐘淵化学工業株式会社 | Graft-modified polyolefin polymer, method for producing the same, and resin composition containing the polymer |
-
1986
- 1986-07-31 JP JP18116286A patent/JPS6337109A/en active Granted
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0522163A1 (en) * | 1990-03-28 | 1993-01-13 | MITSUI TOATSU CHEMICALS, Inc. | Modified polyolefin resin composition |
| WO1993007218A1 (en) * | 1990-04-13 | 1993-04-15 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Thermoplastic resin composition and production thereof |
| WO1991017192A1 (en) * | 1990-04-28 | 1991-11-14 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Modified polyolefin polymer, production thereof, and resin composition containing the same |
| US5294673A (en) * | 1990-04-28 | 1994-03-15 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Modified polyolefin polymer, its manufacturing method and resin composition containing it |
| JP2772870B2 (en) * | 1990-04-28 | 1998-07-09 | 鐘淵化学工業株式会社 | Graft-modified polyolefin polymer, method for producing the same, and resin composition containing the polymer |
| WO1992009643A1 (en) * | 1990-11-30 | 1992-06-11 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Vinylic polymer and production thereof |
| JPH04202513A (en) * | 1990-11-30 | 1992-07-23 | Kanegafuchi Chem Ind Co Ltd | Polyvinyl-based polymer and production thereof |
| US5728791A (en) * | 1990-11-30 | 1998-03-17 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Polyvinyl graft-polymers and manufacturing method thereof |
| WO1993007215A1 (en) * | 1991-10-01 | 1993-04-15 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Thermoplastic resin composition and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0577683B2 (en) | 1993-10-27 |
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