JPS6392636A - Production of modified epoxy resin - Google Patents
Production of modified epoxy resinInfo
- Publication number
- JPS6392636A JPS6392636A JP23854486A JP23854486A JPS6392636A JP S6392636 A JPS6392636 A JP S6392636A JP 23854486 A JP23854486 A JP 23854486A JP 23854486 A JP23854486 A JP 23854486A JP S6392636 A JPS6392636 A JP S6392636A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- allyl alcohol
- reaction
- modified epoxy
- epoxy
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 125000003700 epoxy group Chemical group 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 7
- 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 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 abstract 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 oxyalkylene diol Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- UALAKBZSBJIXBP-UHFFFAOYSA-N 1-phenylethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)(O)C1=CC=CC=C1 UALAKBZSBJIXBP-UHFFFAOYSA-N 0.000 description 1
- BZUILZIKDIMXBK-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCC1OC1 BZUILZIKDIMXBK-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はアリルアルコール変性エポキシｍ 脂ニ関する
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an allyl alcohol modified epoxy resin.
（従来の技術）
エポキシ樹脂とは通常エポキシ基を２個以上もった初期
縮合樹脂を意味し、たとえば、ビスフェノール類やポリ
フェノール類とエピクロルヒドリンの反応で得られる。(Prior Art) Epoxy resin usually means an initial condensation resin having two or more epoxy groups, and is obtained, for example, by the reaction of bisphenols or polyphenols with epichlorohydrin.
従来、エポキシ樹脂は一般にエポキシ樹脂と硬化剤の二
液を組合せて需要家に供給されている。Conventionally, epoxy resins have generally been supplied to consumers as a combination of two components: an epoxy resin and a curing agent.
その使用に当っては二液を均一に混合しなければならな
い。そこで、−液の形で使用できるようにするためにア
クリル酸で変性したエポキシ樹脂が開発されており、こ
の樹脂はラジカル開始剤で容易に重合硬化する。When using it, the two liquids must be mixed uniformly. Therefore, an epoxy resin modified with acrylic acid has been developed so that it can be used in liquid form, and this resin is easily polymerized and cured with a radical initiator.
（発明の解決しようとする問題点）
しかしながら、二液型においては同時に二液を均一に混
合するという煩雑な作業を要し、また現場作業において
は必ずしも均一に混合されないため、硬化後の樹脂の物
性に欠陥を生ずることがある。さらに上記の二液は混合
されると同時に硬化反応が始まるため、混合および加工
時間に限度があり、これを越えると加工困難となり、加
工後の樹脂の物性にも影響を及ぼす。−散型においては
重合可能な二重結合を有するアクリル酸残基がエステル
結合でエポキシ基に導入されているので、重合硬化物は
耐熱性、耐薬品性などにおいて分子構造に由来する弱点
を有する。(Problems to be solved by the invention) However, in the two-component type, it is necessary to mix the two components uniformly at the same time, which is a complicated work, and because the mixture is not always uniform during on-site work, the resin after curing is May cause defects in physical properties. Furthermore, since the curing reaction begins as soon as the two liquids are mixed, there is a limit to the mixing and processing time, and if this time is exceeded, processing becomes difficult and the physical properties of the resin after processing are also affected. - In the dispersed form, an acrylic acid residue with a polymerizable double bond is introduced into the epoxy group through an ester bond, so the polymerized cured product has weaknesses in heat resistance, chemical resistance, etc. due to its molecular structure. .
（問題点を解決するための手段）
本発明者らは従来のエポキシ樹脂がもつ上記のような固
有の欠点を克服するため鋭意研究の結果、本発明に到達
した。(Means for Solving the Problems) The present inventors have arrived at the present invention as a result of intensive research to overcome the above-mentioned inherent drawbacks of conventional epoxy resins.
本発明は、エポキシ樹脂をアリルアルコールと反応させ
ることを特徴とするアリルアルコール変性エポキシ樹脂
の製造法である。The present invention is a method for producing an allyl alcohol-modified epoxy resin, which is characterized by reacting an epoxy resin with allyl alcohol.
エポキシ樹脂としては、一般にエポキシ樹脂と称される
ものを用いうる。エポキシ樹脂は種々の型に分類される
が、いかなる型でも分子中に少くとも２ヶ以上のエポキ
シ基を有するものであればよい。その例としては、ビス
フェノールＡ型、同Ｆ型、同Ｓ型、ハロゲンビスフェノ
ール型、レゾルシン型、テトラヒドロキシフェニルエタ
ン型、ノボラック型、オキシアルキレンジオール型、グ
リセリントリエーテル型、ポリオレフィン型、ポリヒド
ロキシベンゼン型、フタル酸グリシジルエステルなどの
グリシジルエステル型、脂環型、グリシジルアミン型な
どのエポキシ樹脂が挙げられる。As the epoxy resin, what is generally called an epoxy resin can be used. Epoxy resins are classified into various types, but any type may be used as long as it has at least two or more epoxy groups in the molecule. Examples include bisphenol A type, bisphenol F type, bisphenol S type, halogen bisphenol type, resorcinol type, tetrahydroxyphenylethane type, novolak type, oxyalkylene diol type, glycerin triether type, polyolefin type, and polyhydroxybenzene type. , epoxy resins of glycidyl ester type such as phthalic acid glycidyl ester, alicyclic type, and glycidyl amine type.
本発明の反応においてはエポキシ樹脂にアリルアルコー
ルが付加されるが、その反応に用いられるアリルコール
の望ましい量はエポキシ基１当量に対して約１−１０モ
ル倍量の範囲である。しかし、エポキシ樹脂が液状の場
合は１〜１．５モル倍量で充分である。In the reaction of the present invention, allyl alcohol is added to the epoxy resin, and the desirable amount of allyl alcohol used in the reaction is in the range of about 1 to 10 moles per equivalent of epoxy group. However, when the epoxy resin is in liquid form, a 1 to 1.5 molar amount is sufficient.
エポキシ樹脂が固型の場合はメチルイソブチルケトン、
トルエン、キシレンなどの溶媒に溶かして反応させても
よい。If the epoxy resin is solid, methyl isobutyl ketone,
The reaction may be carried out by dissolving it in a solvent such as toluene or xylene.
反応はＢＦ８もしくはその錯体、ＫＯＨ１Ｓｎ Ｃ１！
４などのようなアルコール付加反応用の触媒の存在下
に促進される。触媒の使用量はエポキシ基１当量に対し
て、好ましくは０．０５〜５モル％の範囲である。The reaction is BF8 or its complex, KOH1Sn C1!
4 and the like in the presence of a catalyst for the alcohol addition reaction. The amount of catalyst used is preferably in the range of 0.05 to 5 mol % based on 1 equivalent of epoxy group.
本発明の反応は２０〜１５０℃、好ましくは４０〜１０
０℃の範囲の温度で、１〜２０時間、実質的に無水の状
態で実施するのがよい。The reaction of the present invention is carried out at 20-150°C, preferably at 40-10°C.
It is preferred to carry out in substantially anhydrous conditions at a temperature in the range of 0° C. for 1 to 20 hours.
反応終了後、反応混合物から過剰のアリルアルコールお
よび、場合により、溶媒を留去すれば目的物が残留する
。所望により、残留物を、メチルイソブチルケトンその
他の適当な溶媒に溶解し水洗して触媒を除去し、次いセ
溶媒を留去して目的のアリルアルコール変性エポキシ樹
脂を高収率で得ることもできる。After the reaction is completed, excess allyl alcohol and, if necessary, the solvent are distilled off from the reaction mixture to leave the desired product. If desired, the residue may be dissolved in methyl isobutyl ketone or other suitable solvent, washed with water to remove the catalyst, and then the sesolvent may be distilled off to obtain the desired allyl alcohol-modified epoxy resin in high yield. can.
かくして得られるアリルアルコール変性エポキシ樹脂は
原料のエポキシ樹脂と異なりラジカル開始剤によって容
易に重合硬化する。ラジカル開始剤は、通常ラジカル型
重合を行う際に用いられるものでよく、たと几ば、ベン
ゾイルパーオキサイドなどの過酸化物、アゾビスイソブ
チロニトリル、空気、電子線、紫外線、放射線などが挙
げられる。Unlike the raw material epoxy resin, the allyl alcohol-modified epoxy resin thus obtained is easily polymerized and cured by a radical initiator. The radical initiator may be one that is normally used in radical polymerization, such as peroxides such as benzoyl peroxide, azobisisobutyronitrile, air, electron beams, ultraviolet rays, radiation, etc. It will be done.
本発明のアリルアルコール変性エポキシ樹脂は単独で重
合させることができる。また、それを本発明の樹脂と共
重合可能な二重結合を有する他の化合物と共重合するこ
とにより、それぞれ原料エポキシ樹脂あるいは他の共重
合モノマーに由来する特性をもつ硬化物を得ることもで
きる。The allyl alcohol-modified epoxy resin of the present invention can be polymerized alone. Furthermore, by copolymerizing it with other compounds having double bonds that are copolymerizable with the resin of the present invention, it is also possible to obtain cured products having characteristics derived from the raw epoxy resin or other copolymerized monomers. can.
本発明で得られる変性エポキシ樹脂を用い１こ重合用組
成物にはラジカル開始剤のほか、必要に応じて、充填剤
、難燃材、熱安定剤、抗酸化剤、滑剤等種々の添加剤を
配合することができる。In addition to a radical initiator, the monopolymerization composition using the modified epoxy resin obtained in the present invention contains various additives such as fillers, flame retardants, heat stabilizers, antioxidants, and lubricants as necessary. can be blended.
（作用）
本発明においてアリルアルコールはエポキシ樹脂のエポ
キシ基に付加してエーテル型のアリルオキシ基を生じ、
樹脂を重合可能にすると共に耐熱性、耐薬品性を付与す
る。(Function) In the present invention, allyl alcohol is added to the epoxy group of the epoxy resin to produce an ether type allyloxy group,
It makes the resin polymerizable and gives it heat resistance and chemical resistance.
（実施例）
以下実施例の形で本発明を説明するが、本発明がこれら
の例に限定されないことは言うまでもない。(Examples) The present invention will be described below in the form of examples, but it goes without saying that the present invention is not limited to these examples.
実施例１
撹拌機、温度計、還流冷却器および滴下装置を付けた四
ツロフラスコにアリルアルコール１１６ｇ、三弗化硼素
エチルエーテル０．３８＆を仕込み、撹拌しながら７０
℃において滴下装置から液状のビスフェノールＡ型エポ
キシ樹脂（エポキシ当量１９０ ）３８０９とアリルア
ルコール１１６ダの混合物を２時間を費して滴下した。Example 1 116 g of allyl alcohol and 0.38 g of boron trifluoride ethyl ether were placed in a four-way flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping device, and the mixture was heated to 70 g with stirring.
A mixture of 3809 d of liquid bisphenol A type epoxy resin (epoxy equivalent: 190) and allyl alcohol 116 d was added dropwise from a dropping device at 2 hours.
さらに１時間同温度で撹拌を続けたのち冷却し、反応液
からロータリー・エバポレーターを用いて未反応のアリ
ルアルコールを留去した。残留液をメチルイソブチルケ
トン（Ｍ Ｉ Ｂ Ｋ ） ８００ ｍＯに溶解し、１
０１００Ｏの水で３回洗浄し、油からロータリー・エバ
ポレータによりＭＩＢＫを留去して、無色粘稠性のアリ
ルアルコール変性エポキシ樹脂４５０ｇを得た。After continuing to stir at the same temperature for an additional hour, it was cooled, and unreacted allyl alcohol was distilled off from the reaction solution using a rotary evaporator. The residual solution was dissolved in 800 mO of methyl isobutyl ketone (M I B K ), and 1
After washing three times with 0.0100 O water, MIBK was distilled off from the oil using a rotary evaporator to obtain 450 g of a colorless viscous allyl alcohol-modified epoxy resin.
この製品の沃素価（ＷｉｚＳ法）は１０１．６であった
。原料の液状エポキシ樹脂の分子量が約３８０であるこ
とから理論値は１０２．３となる。したがって、製品中
ではエポキシ基かはゾ完全にアリルアルコールと反応し
ていることが示される。The iodine value (WizS method) of this product was 101.6. Since the molecular weight of the raw material liquid epoxy resin is about 380, the theoretical value is 102.3. Therefore, it is shown that the epoxy groups have completely reacted with allyl alcohol in the product.
実施例２
例１において得られたアリルアルコール変性エポキシ樹
脂２０ｇと過酸化ベンゾイル０．１ｇを１’ ００ ｍ
（！の三角フラスコにとり、１５０℃でマグネチック・
スターラーで撹拌した。２時間を経過したとき内容物が
増粘し、その後局もなく撹拌が停止し、固化が起った。Example 2 20 g of the allyl alcohol-modified epoxy resin obtained in Example 1 and 0.1 g of benzoyl peroxide were mixed in a 1'00 m
(!Pour it into an Erlenmeyer flask and heat it magnetically at 150℃.
Stir with a stirrer. After 2 hours, the contents thickened, and then stirring stopped without any problems, and solidification occurred.
実施例３
例１において得られたアリルアルコール変性エポキシ樹
脂２０１を１００７７Ｌｌの三角フラスコにとり、１５
０℃で空気に接触させながら、空気を巻き込むように激
しく撹拌し続けた。３時間で増粘が始まり、その後間も
なく撹拌が停止し、内容物が固化した。Example 3 Allyl alcohol-modified epoxy resin 201 obtained in Example 1 was placed in a 10,077 L Erlenmeyer flask, and 15
While contacting with air at 0° C., vigorous stirring was continued so as to incorporate air. Thickening began in 3 hours, and shortly thereafter stirring stopped and the contents solidified.
実施例４
例１において得られたアリルアルコール変性エポキシ化
合物２０ｇを１００ ｍｌの三角フラスコにとり、１５
０℃で空気に接触させながら２時間３０分激しく撹拌し
重合反応を行わせた。次いで重合液体を室温まで冷却し
、過剰のメタノールで未重合物を抽出し、残留物として
メタノール含有のモチ状重合物を得た。この重合物をガ
ラス板状に薄く延伸し、６０℃で８時間、さらに１００
℃で２時間乾燥し、フレーク状の透明な固形物としてプ
レポリマー６．５）を得た。氷晶の沃素価は、５０であ
った。Example 4 20 g of the allyl alcohol-modified epoxy compound obtained in Example 1 was placed in a 100 ml Erlenmeyer flask, and
The polymerization reaction was carried out at 0° C. by vigorously stirring for 2 hours and 30 minutes while contacting with air. Next, the polymerization liquid was cooled to room temperature, and unpolymerized materials were extracted with excess methanol to obtain a methanol-containing sticky polymer as a residue. This polymer was stretched thinly into a glass plate shape, heated at 60°C for 8 hours, and further stretched at 100°C.
After drying at ℃ for 2 hours, prepolymer 6.5) was obtained as a flaky transparent solid. The iodine value of the ice crystals was 50.
（発明の効果）
本発明によって得られるアリルアルコール変性エポキシ
樹脂は、従来の二液組み合せて使用するエポキシ樹脂に
おける作業上の時間的な制約、煩雑な加工および硬化物
の物性の不均一などの難点が解消され、作業が容易で、
硬化物の物性も均一となる。(Effects of the Invention) The allyl alcohol-modified epoxy resin obtained by the present invention has the disadvantages of conventional epoxy resins that are used in combination of two components, such as operational time constraints, complicated processing, and nonuniform physical properties of the cured product. This eliminates the problem and makes the work easier.
The physical properties of the cured product also become uniform.
本発明において原料エポキシ樹脂としてエーテル型のエ
ポキシ樹脂を用いて得られる変性エポキシ樹脂は、従来
のアクリル酸変性エポキシ樹脂と異なり、分子中にエス
テル結合が存在しないため、耐熱性、耐薬品性にすぐれ
た硬化物を与えることができる。In the present invention, the modified epoxy resin obtained by using an ether-type epoxy resin as the raw material epoxy resin has excellent heat resistance and chemical resistance because, unlike conventional acrylic acid-modified epoxy resin, there is no ester bond in the molecule. A cured product can be obtained.
本発明により得られる変性エポキシ樹脂においては原料
エポキシ樹脂に比ベアリル基の鎖が長いため、硬化物に
可撓性を付与することができ、まｊこエポキシ基にアリ
ルアルコールが付加して一〇Ｈ基が生ずるため接着性が
向上する。したがって、他のビニルモノマーもしくはア
リルモノマーまたはこれらのプレポリマーと共重合する
ことにより、これらのモノマーもしくはプレポリマー単
独の重合硬化物に比べ可撓性、接着性のすぐれた硬化物
を与えるＯとができる。すなわら、他のビニルあるいは
アリル系重合物の改質材として有用である。In the modified epoxy resin obtained by the present invention, the chain of bearyl groups is longer than that of the raw material epoxy resin, so it is possible to impart flexibility to the cured product, and allyl alcohol is added to the epoxy group. Adhesion is improved due to the generation of H groups. Therefore, by copolymerizing with other vinyl monomers or allyl monomers or their prepolymers, O can provide a cured product with superior flexibility and adhesiveness compared to the polymerized cured product of these monomers or prepolymers alone. can. In other words, it is useful as a modifier for other vinyl or allyl polymers.
本発明により得られる変性エポキシ樹脂をモノマーとし
てラジカル重合させ、硬化が起る寸前で重合を中止し、
重合反応混合物からメタノールのような抽出剤により未
重合モノマーを除去すると、あとにプレポリマーが析出
する。このプレポリマーはそれ単独で、あるいはそれと
共重合しうるモノマーもしくはプレポリマーまたは充填
剤などと共に、さらに重合させ硬化させれば工業上有用
な成形品、接着剤などが得られる。The modified epoxy resin obtained by the present invention is radically polymerized as a monomer, and the polymerization is stopped just before curing occurs,
Unpolymerized monomers are removed from the polymerization reaction mixture by an extractant such as methanol, which subsequently precipitates the prepolymer. If this prepolymer is further polymerized and cured alone or together with monomers, prepolymers, fillers, etc. that can be copolymerized with it, industrially useful molded products, adhesives, etc. can be obtained.
Claims (1)
徴とするアリルアルコール変性エポキシ樹脂の製造法。A method for producing an allyl alcohol-modified epoxy resin, which comprises reacting an epoxy resin with allyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23854486A JPS6392636A (en) | 1986-10-06 | 1986-10-06 | Production of modified epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23854486A JPS6392636A (en) | 1986-10-06 | 1986-10-06 | Production of modified epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6392636A true JPS6392636A (en) | 1988-04-23 |
Family
ID=17031828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23854486A Pending JPS6392636A (en) | 1986-10-06 | 1986-10-06 | Production of modified epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6392636A (en) |
-
1986
- 1986-10-06 JP JP23854486A patent/JPS6392636A/en active Pending
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