JPS63265912A - Manufacture of novel epoxy resin - Google Patents
Manufacture of novel epoxy resinInfo
- Publication number
- JPS63265912A JPS63265912A JP10056487A JP10056487A JPS63265912A JP S63265912 A JPS63265912 A JP S63265912A JP 10056487 A JP10056487 A JP 10056487A JP 10056487 A JP10056487 A JP 10056487A JP S63265912 A JPS63265912 A JP S63265912A
- Authority
- JP
- Japan
- Prior art keywords
- epichlorohydrin
- group
- compound
- hydroxyl group
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 32
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 18
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 6
- -1 epichlorohydrin compound Chemical class 0.000 claims abstract description 6
- 239000002841 Lewis acid Substances 0.000 claims abstract description 5
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 5
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 5
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- 239000012442 inert solvent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000011033 desalting Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 abstract description 8
- 229960003656 ricinoleic acid Drugs 0.000 abstract description 8
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003607 modifier Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 3
- 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 3
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は新規なエポキシ樹脂の製造法に関するものであ
る。さらに詳しくは、一分子内に１個以上のアルコール
性水酸基と、 １個以上のカルボキシル基またはフェノ
ール性水酸基を持つ化合物のエポキシ化方法に間するも
のである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel method for producing epoxy resins. More specifically, it is a method for epoxidizing a compound having one or more alcoholic hydroxyl groups and one or more carboxyl groups or phenolic hydroxyl groups in one molecule.
［従来の技術］
一般にエポキシ樹脂の製造方法にはエポキシ化しようと
する官能基に応じて何通りかの方法が考案されている。[Prior Art] Generally, several methods have been devised for producing epoxy resins depending on the functional group to be epoxidized.
それらを官能基側に分類するとフルコール性水酸基、カ
ルボキシル基、フェノール性水酸基、アミノ基、不飽和
基などに分類され、それぞれに応じたエポキシ化方法が
採用されている。そのうちアルコール性水酸基はルイス
酸触媒を用い、エピクロルヒドリンを付加させる方法で
、カルボキシル基及びフェノール性水酸基は第４級アン
モニウム塩触媒を用い、エピクロルヒドリンを付加させ
る方法で、それぞれ該当するクロルヒドリン化合物とし
、その後、水酸化アルカリを用いてエポキシ基とすると
いう合成法が最も一般的な方法である。When classified into functional groups, they are classified into flucolic hydroxyl groups, carboxyl groups, phenolic hydroxyl groups, amino groups, unsaturated groups, etc., and epoxidation methods are adopted depending on each group. Among them, the alcoholic hydroxyl group is added with epichlorohydrin using a Lewis acid catalyst, and the carboxyl group and phenolic hydroxyl group are added with epichlorohydrin using a quaternary ammonium salt catalyst to form the corresponding chlorohydrin compound, and then, The most common method is to use an alkali hydroxide to form an epoxy group.
ところが、今まで一分子内にアルコール性水酸基とカル
ボキシル基またはフェノール性水酸基の両方を持つ化合
物について、その両方を同時にエポキシ化することは非
常に困難であるとされていた。その理由としては、カル
ボキシル基やフェノール性水酸基の方がアルコール性水
酸基よりも酸性度が強く、エピクロルヒドリンと反応さ
せる場合には前者の方により選択的に反応すると考えら
れていたためである。However, until now, it has been considered extremely difficult to simultaneously epoxidize a compound having both an alcoholic hydroxyl group and a carboxyl group or a phenolic hydroxyl group in one molecule. The reason for this is that carboxyl groups and phenolic hydroxyl groups are more acidic than alcoholic hydroxyl groups, and when reacted with epichlorohydrin, it was thought that the former would react more selectively.
［発明の開示］
本発明では、一分子内にアルコール性水酸基とカルボキ
シル基またはフェノール性水酸基を持つ化合物に対し、
ルイス酸触媒を用いることにより、アルコール性水酸基
の方にほぼ選択的にエピクロルヒドリンを反応させ得る
ことを発見し、それを利用して両者を同時にエポキシ化
する方法を考案したものである。[Disclosure of the Invention] In the present invention, for a compound having an alcoholic hydroxyl group and a carboxyl group or a phenolic hydroxyl group in one molecule,
They discovered that by using a Lewis acid catalyst, epichlorohydrin could react almost selectively with alcoholic hydroxyl groups, and devised a method that utilized this to simultaneously epoxidize both alcoholic hydroxyl groups.
即ち、まず、不活性溶媒中、または無溶媒下、ルイス酸
触媒を用いてアルコール性水酸基にほぼ選択的にエピク
ロルヒドリンを反応させる０次に水酸化アルカリなどで
ルイス酸を中和し、カルボキシル基またはフェノール性
水酸基に対し、過剰のエピクロルヒドリンを添加し、第
４縁アンモニウム塩触媒などを用いてカルボキシル基ま
たはフェノール性水酸基にエピクロルヒドリンを付加さ
せる。さらに水酸化アルカリを用いて生成したクロルヒ
ドリン化合物をエポキシ基とする。そして、公知の方法
により脱塩、脱エピクロルヒドリンを行い、目的とする
エポキシ樹脂を得る。なお、さらに公知の方法で精製を
目的とした２次処理を行うことは何らさしつかえない。That is, first, epichlorohydrin is almost selectively reacted with alcoholic hydroxyl groups using a Lewis acid catalyst in an inert solvent or without a solvent.Next, the Lewis acid is neutralized with an alkali hydroxide or the like, and the carboxyl group or Excess epichlorohydrin is added to the phenolic hydroxyl group, and epichlorohydrin is added to the carboxyl group or the phenolic hydroxyl group using a fourth edge ammonium salt catalyst or the like. Furthermore, a chlorohydrin compound produced using an alkali hydroxide is converted into an epoxy group. Then, desalting and epichlorohydrin removal are performed by a known method to obtain the desired epoxy resin. In addition, there is no problem in performing further secondary treatment for the purpose of purification using a known method.
本発明におけるエポキシ化の原料となる化合物は、一分
子内にアルコール性水酸基を１個以上持ち、カルボキシ
ル基またはフェノール性水酸基を１個以上持つものであ
ればほとんどすべてのものについて適用できるが、好ま
しくは、リシノール酸、１２−ヒドロキシステアリン酸
、グリコール酸、乳酸、４−ヒドロキシ酪酸、６−ヒド
ロキシカプロン酸、ｐ−ヒドロキシフェネチルアルコー
ルが有用である。The compound serving as a raw material for epoxidation in the present invention can be applied to almost any compound as long as it has one or more alcoholic hydroxyl group and one or more carboxyl group or phenolic hydroxyl group in one molecule, but it is preferable. Useful examples include ricinoleic acid, 12-hydroxystearic acid, glycolic acid, lactic acid, 4-hydroxybutyric acid, 6-hydroxycaproic acid, and p-hydroxyphenethyl alcohol.
本発明で用いられる不活性溶媒にはベンゼン、トルエン
、キシレンなどの芳香族系炭化水素やｎ−ヘキサン、シ
クロヘキサンなどの脂肪族系炭化水素などがあるが特に
限定するものではない、また、ルイス酸としては三フッ
化ホウ素エーテル錯塩、四塩化錫、塩化アルミニウム、
塩化鉄、塩化亜鉛などがあるが、特に限定するものでは
ない。Inert solvents used in the present invention include, but are not particularly limited to, aromatic hydrocarbons such as benzene, toluene, and xylene, and aliphatic hydrocarbons such as n-hexane and cyclohexane. Examples include boron trifluoride ether complex, tin tetrachloride, aluminum chloride,
Examples include iron chloride and zinc chloride, but they are not particularly limited.
ルイス酸の中和には水酸化ナトリウム、水酸化カリウム
、炭酸ナトリウム、炭酸カリウムなどが使用可能である
が、ルイス酸を中和できるものであれば特に限定するも
のではない、カルボキシル基またはフェノール性水酸基
とエピクロルヒドリンとの反応触媒も数多くのものが知
られている。トリエチルベンジルアンモニウムクロライ
ド、テトラメチルアンモニウムクロライド、トリエチル
アミンなどがであるが、これらを反応させる能力のある
触媒であれば特に限定するものではない。Sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. can be used to neutralize Lewis acids, but there are no particular limitations as long as they can neutralize Lewis acids. Many catalysts for the reaction between hydroxyl groups and epichlorohydrin are also known. Examples include triethylbenzylammonium chloride, tetramethylammonium chloride, triethylamine, etc., but there are no particular limitations as long as the catalyst is capable of reacting these.
本発明によって新たにリシノール酸、 １２−ヒドロキ
システアリン酸のアルコール性水酸基及びカルボキシル
基の両方がエポキシ化されたグリシジルエーテル・エス
テル型エポキシ樹脂の製造が可能になった。該エポキシ
樹脂は長鎖アルキレン基またはアルケニレン基を持つた
め、可撓性、耐水性に優れかつ低粘度であるという非常
に有用なエポキシ樹脂であり、改質剤としてその応用範
囲は非常に広い、 例えば、エポキシ樹脂の改質はも
ちろん、フェノール樹脂や不飽和ポリエステル樹脂など
の熱硬化性樹脂、ＰＶＣ、ポリオレフィン、ポリエステ
ル、アクリル樹脂などの熱可塑性樹脂の改質に極めて有
用である。特に、フェノール樹脂には桐油、ＰｖＣには
エポキシ化大豆油が改質剤として用いられているが、該
エポキシ樹脂は、これらと同様に油脂系改質剤としての
効果が貼待できる。The present invention has newly made it possible to produce a glycidyl ether ester type epoxy resin in which both the alcoholic hydroxyl group and carboxyl group of ricinoleic acid and 12-hydroxystearic acid are epoxidized. Since the epoxy resin has a long-chain alkylene group or alkenylene group, it is a very useful epoxy resin that has excellent flexibility, water resistance, and low viscosity, and has a very wide range of applications as a modifier. For example, it is extremely useful for modifying not only epoxy resins but also thermosetting resins such as phenolic resins and unsaturated polyester resins, and thermoplastic resins such as PVC, polyolefins, polyesters, and acrylic resins. In particular, tung oil is used as a modifier for phenol resin, and epoxidized soybean oil is used as a modifier for PvC, and the epoxy resin can be applied as an oil-based modifier in the same way as these.
［実施例］
以下に本発明の詳細な説明するが、本発明はこれらの実
施例に限定されるものではない。[Examples] The present invention will be described in detail below, but the present invention is not limited to these Examples.
実施例１
攪拌機、温度計、滴下ロート、コンデンサーを備えた四
つロフラスコにリシノール酸（オレイン酸、分子間縮合
物などの不純物を約１０重量％含有する。）３４４部、
三フッ化ホウ素エーテル錯塩０．７部を仕込み、６０℃
まで加熱する。滴下ロートより、エピクロルヒドリン１
４８部を内温か６０〜７０℃を保つように約１時間かけ
て滴下し、さらに同温度で３０分反応を続ける。 その
後、４８％水酸化ナトリウム水溶液１部を添加し、三フ
ッ化ホウ素エーテル錯塩を中和する。この反応物を解析
したところ、エピクロルヒドリンはリシノール酸のアル
コール性水酸基にほぼ選択的に反応しており、カルボキ
シル基にはあまり反応していなかった。 （反応比率は
ほぼ８：２であった。）さらに、同フラスコにエピクロ
ルヒドリン７４０部、トリエチルベンジルアンモニウム
クロライド３部を添加し、１００℃で１時閏反応させた
ところ、リシノール酸のカルボキシル基は完全にエピク
ロルヒドリンと反応していた。４０℃まで冷却後、４８
％水酸化ナトリウム水溶液１５０部な同温度で滴下ロー
トより約１時間かけて滴下し、さらに同温度で３０分反
応を続ける。生成塩を水洗除去した後、同様に４８％水
酸化ナトリウム６７部で２次処理を行い、生成塩を水洗
除去する。さらにイオン交換水で数回洗浄し、減圧下、
過剰のエピクロルヒドリンを留去すると４８４部の淡黄
色透明液状のエポキシ樹脂が得られた。この樹脂のエポ
キシ当量は２９５であり、２５℃における粘度は６３セ
ンチボイズであった。Example 1 344 parts of ricinoleic acid (containing about 10% by weight of impurities such as oleic acid and intermolecular condensates) was placed in a four-loaf flask equipped with a stirrer, thermometer, dropping funnel, and condenser.
Add 0.7 part of boron trifluoride ether complex salt and heat at 60°C.
Heat until. From the dropping funnel, add 1 part of epichlorohydrin.
48 parts were added dropwise over about 1 hour while keeping the internal temperature at 60 to 70°C, and the reaction was continued at the same temperature for an additional 30 minutes. Then, 1 part of a 48% aqueous sodium hydroxide solution is added to neutralize the boron trifluoride ether complex salt. Analysis of this reaction product revealed that epichlorohydrin reacted almost selectively with the alcoholic hydroxyl group of ricinoleic acid, and did not react much with the carboxyl group. (The reaction ratio was approximately 8:2.) Furthermore, 740 parts of epichlorohydrin and 3 parts of triethylbenzylammonium chloride were added to the same flask, and a leap reaction was carried out at 100°C for 1 hour. As a result, the carboxyl group of ricinoleic acid was completely removed. reacted with epichlorohydrin. After cooling to 40℃, 48
% sodium hydroxide aqueous solution was added dropwise from the dropping funnel at the same temperature over about 1 hour, and the reaction was further continued at the same temperature for 30 minutes. After removing the salt produced by washing with water, a secondary treatment is similarly performed with 67 parts of 48% sodium hydroxide, and the salt produced is removed by washing with water. Furthermore, it was washed several times with ion-exchanged water, and then washed under reduced pressure.
Excess epichlorohydrin was distilled off to obtain 484 parts of a pale yellow transparent liquid epoxy resin. The epoxy equivalent weight of this resin was 295, and the viscosity at 25°C was 63 centivoise.
実施例２
実施例１でリシノール酸の代わりに１２−ヒドロキシス
テアリン酸３５５部、溶媒としてトルエン１００部を用
いる以外は同様の操作を行ったところ４９９部の淡黄色
透明で融点が約２０℃のエポキシ樹脂が得られた。この
樹脂のエポキシ当量は２９０であフた。Example 2 The same procedure as in Example 1 was performed except that 355 parts of 12-hydroxystearic acid was used instead of ricinoleic acid and 100 parts of toluene was used as the solvent. 499 parts of a pale yellow transparent epoxy with a melting point of about 20°C was obtained. A resin was obtained. The epoxy equivalent of this resin was 290.
比較例
同フラスコにてリシノール酸３４４部と、エピクロルヒ
ドリン７４０部とを、トリエチルベンジルアンモニウム
クロライド３部を触媒として反応させ、４８％水酸化ナ
トリウム水溶液で処理したが、リシノール酸のアルコー
ル性水酸基は全くエポキシ化されていなかった。Comparative Example In the same flask, 344 parts of ricinoleic acid and 740 parts of epichlorohydrin were reacted using 3 parts of triethylbenzylammonium chloride as a catalyst, and the mixture was treated with a 48% aqueous sodium hydroxide solution. It had not been standardized.
［発明の効果］
本発明により、今までエポキシ化できなかったものがエ
ポキシ化できるようになった。その中ζこは、改質剤、
可撓性付与剤、反応性希釈剤として有用なものが多数存
在する。[Effects of the Invention] According to the present invention, materials that could not be epoxidized up to now can now be epoxidized. Among them, ζ is a modifier,
There are many useful flexibility-imparting agents and reactive diluents.
Claims (1)
に１個以上のアルコール性水酸基と１個以上のカルボキ
シル基、またはフェノール性水酸基を持つ化合物に対し
、ルイス酸触媒を用いてアルコール性水酸基にほぼ選択
的にエピクロルヒドリンを付加させる工程。 〈第２工程〉ルイス酸を水酸化アルカリなどで中和した
後、カルボキシル基またはフェノール性水酸基に対し、
過剰のエピクロルヒドリンを添加し、第４級アンモニウ
ム塩触媒などを用いて、カルボキシル基またはフェノー
ル性水酸基にエピクロルヒドリンを付加させる工程。 〈第３工程〉水酸化アルカリを用いて、生成したクロル
ヒドリン化合物をエポキシ基とし、公知の方法により脱
塩、脱エピクロルヒドリンを行う工程。 からなる新規なエポキシ樹脂の製造法。[Claims] <First step> In an inert solvent or in the absence of a solvent, for a compound having one or more alcoholic hydroxyl groups and one or more carboxyl groups or phenolic hydroxyl groups in one molecule, A process in which epichlorohydrin is almost selectively added to alcoholic hydroxyl groups using a Lewis acid catalyst. <Second step> After neutralizing the Lewis acid with an alkali hydroxide etc., the carboxyl group or phenolic hydroxyl group is
A step of adding an excess of epichlorohydrin and adding epichlorohydrin to a carboxyl group or phenolic hydroxyl group using a quaternary ammonium salt catalyst or the like. <Third Step> A step of converting the generated chlorohydrin compound into an epoxy group using alkali hydroxide, and performing desalting and removal of epichlorohydrin by a known method. A new method for producing epoxy resin consisting of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10056487A JPS63265912A (en) | 1987-04-22 | 1987-04-22 | Manufacture of novel epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10056487A JPS63265912A (en) | 1987-04-22 | 1987-04-22 | Manufacture of novel epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63265912A true JPS63265912A (en) | 1988-11-02 |
Family
ID=14277414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10056487A Pending JPS63265912A (en) | 1987-04-22 | 1987-04-22 | Manufacture of novel epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63265912A (en) |
-
1987
- 1987-04-22 JP JP10056487A patent/JPS63265912A/en active Pending
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