JPH0515751B2 - - Google Patents
Info
- Publication number
- JPH0515751B2 JPH0515751B2 JP22812187A JP22812187A JPH0515751B2 JP H0515751 B2 JPH0515751 B2 JP H0515751B2 JP 22812187 A JP22812187 A JP 22812187A JP 22812187 A JP22812187 A JP 22812187A JP H0515751 B2 JPH0515751 B2 JP H0515751B2
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- reaction
- epihalohydrin
- glycidyl ester
- alkali
- 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.)
- Expired - Lifetime
Links
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 56
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 56
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 56
- -1 glycidyl ester Chemical class 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003840 hydrochlorides Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-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
- 239000007864 aqueous solution Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000003944 halohydrins Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OIFAHDAXIUURLN-UHFFFAOYSA-N 2-(fluoromethyl)oxirane Chemical compound FCC1CO1 OIFAHDAXIUURLN-UHFFFAOYSA-N 0.000 description 1
- AGIBHMPYXXPGAX-UHFFFAOYSA-N 2-(iodomethyl)oxirane Chemical compound ICC1CO1 AGIBHMPYXXPGAX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明はロジングリシジルエステルの製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing rosin glycidyl ester.
[従来の技術]
ロジングリシジルエステルは、アルキツド樹脂
の改質剤、接着剤の原料、ポリエステルの原料、
エポキシ樹脂の希釈剤などの用途に使用されてい
る有用な化合物である。[Prior art] Rosin glycidyl ester is used as a modifier for alkyd resins, a raw material for adhesives, a raw material for polyester,
It is a useful compound used as a diluent for epoxy resins.
一般にカルボン酸グリシジルエステルは過剰量
のエピハロヒドリンとカルボン酸またはそのアル
カリ金属塩とを塩基性触媒とともに常圧下で加熱
反応させる方法により製造されている。 Generally, carboxylic acid glycidyl esters are produced by a method in which an excess amount of epihalohydrin and a carboxylic acid or an alkali metal salt thereof are subjected to a heating reaction together with a basic catalyst under normal pressure.
しかしながら、ロジンにおいてはエピハロヒド
リンと反応するカルボキシル基が嵩高いヒドロフ
エナンスレン核の第3級炭素に結合しており、そ
の立体障害ゆえ反応性が低下するため常圧下での
反応は困難であると考えられている。従来より、
ロジングリシジルエステルを製造する方法として
は、ロジンのナトリウム塩(ロジン石鹸)と過剰
量のエピハロヒドリンとを水の不存在下で加圧容
器中、約180℃に加熱して製造する方法が知られ
ているが、この方法では加圧、高温を必須とする
ため工業的に不利である。 However, in rosin, the carboxyl group that reacts with epihalohydrin is bonded to the tertiary carbon of the bulky hydrophenanthrene nucleus, and its steric hindrance reduces reactivity, making it difficult to react under normal pressure. It is considered. Traditionally,
A known method for producing rosin glycidyl ester is to heat rosin sodium salt (rosin soap) and an excess amount of epihalohydrin to approximately 180°C in a pressurized container in the absence of water. However, this method requires pressurization and high temperature, which is industrially disadvantageous.
また、ロジングリシジルエステルを常圧下で製
造する方法としては、従来よりアミン類、トリフ
エニルホスフインなどの塩基性触媒とアルカリの
共存下にエピハロヒドリンを反応させる方法が知
られている(特開昭55−80575号公報)。しかし、
かかる方法によるばあいには、ロジンジグリセラ
イドなどの副生物ができ、目的物たるロジングリ
シジルエステルの収率、純度を著しく低下させる
ため工業的製造として使用しがたい。すなわち、
かかる方法ではロジンとエピハロヒドリンを触媒
とアルカリの共存下に反応させるため、ロジンと
エピハロヒドリンとを反応させるハロヒドリンエ
ステル化工程と、ハロヒドリンエステルの脱ハロ
ゲン化水素工程とが同時に存在することとなる。
そのためえられたロジングリシジルエステルと未
反応のロジンがさらに反応してジグリセライドが
生じたものと考えられる。また、前記触媒の活性
は必ずしも充分であるとはいいがたい。 Furthermore, as a method for producing rosin glycidyl ester under normal pressure, a method in which epihalohydrin is reacted in the coexistence of a basic catalyst such as amines or triphenylphosphine with an alkali has been known (Japanese Patent Laid-Open No. 1983-1996). -80575). but,
In the case of such a method, by-products such as rosin diglyceride are produced, and the yield and purity of the target rosin glycidyl ester are significantly reduced, making it difficult to use in industrial production. That is,
In this method, rosin and epihalohydrin are reacted in the presence of a catalyst and an alkali, so that a halohydrin esterification step in which rosin and epihalohydrin are reacted and a dehydrohalogenation step of the halohydrin ester are simultaneously present. Become.
Therefore, it is thought that the obtained rosin glycidyl ester and unreacted rosin further reacted to produce diglyceride. Moreover, it cannot be said that the activity of the catalyst is necessarily sufficient.
[発明が解決しようとする問題点]
本発明はロジングリシジルエステルを常圧下で
しかも高収率かつ高純度で製造する方法を提供す
ることを目的とする。[Problems to be Solved by the Invention] An object of the present invention is to provide a method for producing rosin glycidyl ester under normal pressure with high yield and high purity.
[問題点を解決するための手段]
本発明者らは前記目的を達成するべく鋭意検討
を重ねた結果、触媒としてアミンと強酸とからえ
られる酸性の特定アミン塩を用い、かつ後述する
2段階反応を経由させたばあいには初めて前記問
題点がことごとく解決されうることを見出し本発
明を完成するに至つた。[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors used a specific acidic amine salt obtained from an amine and a strong acid as a catalyst, and carried out the two-step process described below. The present inventors have discovered that all of the above problems can be solved for the first time through a reaction, and have completed the present invention.
すなわち、本発明はロジンとエピハロヒドリン
をアミン塩の存在下に反応させてロジンエピハロ
ヒドリンエステルとし、ついでアルカリにより脱
ハロゲン化水素することを特徴とするロジングリ
シジルエステルの製造方法に関する。 That is, the present invention relates to a method for producing rosin glycidyl ester, which is characterized by reacting rosin and epihalohydrin in the presence of an amine salt to produce rosin epihalohydrin ester, and then dehydrohalogenating with an alkali.
[実施例]
本発明に用いられるロジンとしては、たとえば
ガムロジン、ウツドロジン、トール油ロジンのご
とき天然ロジンおよび水添ロジン、不均化ロジ
ン、重合ロジンのごとき変性ロジンのいずれも有
効に使用しうる。[Example] As the rosin used in the present invention, for example, any of natural rosins such as gum rosin, oil rosin, and tall oil rosin, and modified rosins such as hydrogenated rosin, disproportionated rosin, and polymerized rosin can be effectively used.
本発明に用いられるエピハロヒドリンとして
は、たとえばエピクロルヒドリン、エピブロムヒ
ドリン、エピヨードヒドリン、エピフルオロヒド
リンなどがあげられるが、工業的にはエピクロル
ヒドリンが好ましい。 Examples of the epihalohydrin used in the present invention include epichlorohydrin, epibromohydrin, epiiodohydrin, and epifluorohydrin, and epichlorohydrin is preferred from an industrial standpoint.
エピハロヒドリンの使用量は、ロジンのカルボ
キシル基が反応後に残らないようにするためにロ
ジンのカルボキシル基と等モル数以上を用いるの
がよい。通常は過剰に用いられ、化学量論量の2
〜10倍量が好ましい。 The amount of epihalohydrin to be used is preferably at least the same molar number as the carboxyl group of the rosin so that the carboxyl group of the rosin does not remain after the reaction. Usually used in excess, stoichiometric
~10 times the amount is preferred.
本発明においては触媒としてアミン塩を用いる
ことが必須とされ、該触媒を用いることにより初
めて本発明の目的が達成されるのである。ここに
触媒としてアミンを用いたばあいにはエステル化
反応触媒としての活性が著しく低く、エピクロル
ヒドリンの沸点である120℃で反応させても反応
を完結させるのに10時間以上という長時間を要す
るため実用性に欠ける。ここでアミン塩とは、ア
ミンにハロゲン酸、硫酸などの強酸を反応させて
えられる酸性化合物のことである。アミン塩とし
ては、第1級アミン塩、第2級アミン塩、第3級
アミン塩、第4級アンモニウム塩のいずれをも有
効に使用することができる。第1級アミン塩の具
体例としては、たとえばメチルアミン、エチルア
ミン、プロピルアミン、ブチルアミン、ベンジル
アミン、アニリンなどの第1級アミンの塩酸塩、
臭化水素酸塩、フツ化水素酸塩、硫酸塩などがあ
げられる。第2級アミン塩の具体例としては、た
とえばジメチルアミン、ジエチルアミン、N−メ
チルアニリン、ベンジルメチルアミンなどの第2
級アミンの塩酸塩、臭化水素酸塩、フツ化水素酸
塩、硫酸塩などがあげられる。第3級アミン塩の
具体例としては、たとえばトリメチルアミン、ト
リエチルアミン、N,N−ジメチルアニリン、ジ
メチルベンジルアミンなどの第3級アミンの塩酸
塩、臭化水素酸塩、フツ化水素酸塩、硫酸塩など
があげられる。また第4級アンモニウム塩の具体
例としては、たとえばテトラメチルアンモニウ
ム、テトラエチルアンモニウム、ベンジルトリエ
チルアンモニウム、アリルトリエチルアンモニウ
ム、テトラブチルアンモニウム、トリメチルベン
ジルアンモニウムなどの各種第4級アミンの塩素
化物、臭素化物、フツ素化物、硫酸塩などがあげ
られる。 In the present invention, it is essential to use an amine salt as a catalyst, and the purpose of the present invention can only be achieved by using this catalyst. When an amine is used as a catalyst, its activity as an esterification reaction catalyst is extremely low, and even if the reaction is carried out at 120°C, which is the boiling point of epichlorohydrin, it takes a long time of 10 hours or more to complete the reaction. Lacks practicality. Here, the amine salt is an acidic compound obtained by reacting an amine with a strong acid such as a halogen acid or sulfuric acid. As the amine salt, any of primary amine salts, secondary amine salts, tertiary amine salts, and quaternary ammonium salts can be effectively used. Specific examples of primary amine salts include hydrochlorides of primary amines such as methylamine, ethylamine, propylamine, butylamine, benzylamine, and aniline;
Examples include hydrobromide, hydrofluoride, and sulfate. Specific examples of secondary amine salts include secondary amine salts such as dimethylamine, diethylamine, N-methylaniline, and benzylmethylamine.
Examples include hydrochlorides, hydrobromides, hydrofluorides, and sulfates of grade amines. Specific examples of tertiary amine salts include hydrochlorides, hydrobromides, hydrofluorides, and sulfates of tertiary amines such as trimethylamine, triethylamine, N,N-dimethylaniline, and dimethylbenzylamine. etc. Specific examples of quaternary ammonium salts include chlorinated, brominated, and Examples include compounds, sulfates, etc.
前記触媒の使用量はロジンに対して0.01〜10重
量%、好ましくは0.05〜1重量%である。該触媒
の使用量は0.01重量%未満であるばあい、エステ
ル化反応の完結に長時間を要することとなり、ま
た10重量%をこえるばあい、何ら有利な点はな
く、経済的に不利なだけである。 The amount of the catalyst used is 0.01 to 10% by weight, preferably 0.05 to 1% by weight, based on the rosin. If the amount of the catalyst used is less than 0.01% by weight, it will take a long time to complete the esterification reaction, and if it exceeds 10% by weight, there will be no advantage and only an economic disadvantage. It is.
また、本発明ではえられたロジンエピハロヒド
リンエステルを脱ハロゲン化水素して目的物たる
ロジングリシジルエステルとするためにアルカリ
を用いることが必須とされる。該アルカリとして
はアルカリ金属の水酸化物が好ましく、かかる具
体例としては、たとえば水酸化ナトリウム、水酸
化カリウム、水酸化リチウムなどがあげられる。
アルカリの使用形態は固形のまま反応系に添加す
るのが好ましいが、水溶液として添加してもよ
い。アルカリを水溶液として用いるばあいにはそ
の濃度が40重量%以上となるように調整して用い
る。40重量%に満たないばあいには、副反応が進
み目的物の収量が低下するためである。アルカリ
の使用量は、ロジンのカルボキシル基1当量に対
して少なくとも1当量、好ましくは1.05〜1.20倍
当量とするのがよい。1当量未満のばあいには反
応は完結しない。1.20倍当量をこえて使用しても
有利な面はなく経済的に不利なだけである。 Further, it is essential to use an alkali to dehydrohalogenate the rosin epihalohydrin ester obtained in the present invention to obtain the desired rosin glycidyl ester. The alkali is preferably an alkali metal hydroxide, and specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like.
The alkali is preferably added to the reaction system in solid form, but it may also be added as an aqueous solution. When an alkali is used as an aqueous solution, its concentration is adjusted to 40% by weight or more. This is because if the amount is less than 40% by weight, side reactions will proceed and the yield of the target product will decrease. The amount of alkali to be used is at least 1 equivalent, preferably 1.05 to 1.20 times the equivalent of carboxyl group of the rosin. If the amount is less than 1 equivalent, the reaction will not be completed. There is no advantage to using more than 1.20 times the equivalent and it is only economically disadvantageous.
本発明のロジングリシジルエステルの製造方法
は、ロジンと過剰量のエピハロヒドリンを前記触
媒の存在下に加熱してハロヒドリンエステル化す
る工程と、該工程でえられたロジンエピハロヒド
リンエステルをアルカリ処理により脱ハロゲン化
水素しオキシラン環を生成する工程の2段階から
なる。第1段階の反応であるハロヒドリンエステ
ル化する工程の反応温度および反応時間は生成物
の収率を考慮して適宜決定されるが、通常は反応
温度50〜120℃、好ましくは80〜100℃、反応時間
1〜10時間、好ましくは1〜4時間である。反応
の終点はHLC(高速液体カラムクロマトグラフイ
ー)測定法により容易に確認することができる
が、第2段階反応への移行は、未反応ロジンが存
在せずロジンのカルボキシル基が完全にハロヒド
リンエステルに転化したことを確認した後に行な
うのがよい。反応系内に未反応ロジンが存在する
ばあいには、該ロジンと脱ハロゲン酸工程でえら
れるロジングリシジルエステルとが反応して副生
物であるロジングリセライドを生成するからであ
る。第2段階の反応である脱ハロゲン酸工程の反
応温度は通常50〜120℃、好ましくは100〜120℃、
反応時間は1〜10時間、好ましくは1〜2時間で
ある。反応の終了は前記と同様にHLC測定法に
より確認すればよい。 The method for producing rosin glycidyl ester of the present invention includes a step of heating rosin and an excess amount of epihalohydrin in the presence of the catalyst to convert the rosin into a halohydrin ester, and removing the rosin epihalohydrin ester obtained in the step by alkali treatment. The process consists of two steps: hydrogen halide and generation of an oxirane ring. The reaction temperature and reaction time of the halohydrin esterification step, which is the first step reaction, are determined appropriately taking into account the yield of the product, but usually the reaction temperature is 50 to 120°C, preferably 80 to 100°C. ℃, and the reaction time is 1 to 10 hours, preferably 1 to 4 hours. The end point of the reaction can be easily confirmed by HLC (high performance liquid column chromatography) measurement method, but the transition to the second stage reaction is when there is no unreacted rosin and the carboxyl group of the rosin is completely converted to halohydride. It is best to carry out this after confirming that it has been converted to phosphorus ester. This is because if unreacted rosin exists in the reaction system, the rosin and the rosin glycidyl ester obtained in the dehalogenation step will react to produce rosin glyceride as a by-product. The reaction temperature of the second stage reaction, the dehalogenation step, is usually 50 to 120°C, preferably 100 to 120°C,
The reaction time is 1 to 10 hours, preferably 1 to 2 hours. Completion of the reaction may be confirmed by HLC measurement in the same manner as above.
すなわち本発明は2段階の反応を行なつて初め
て本目的を達成しうるのである。したがつて、た
とえ本発明の触媒を用いたとしても、これとアル
カリとを同時に添加し反応せしめたばあいには本
発明の目的は達成されず、このばあいには副反応
生成物が増え(反応生成物のエポキシ当量が大き
くなる)、目的生成物の収率、純度を低下させる
結果となる。 In other words, the object of the present invention can only be achieved by carrying out a two-step reaction. Therefore, even if the catalyst of the present invention is used, the object of the present invention will not be achieved if the catalyst and an alkali are simultaneously added and reacted, and in this case, side reaction products will increase. (The epoxy equivalent of the reaction product increases), resulting in a decrease in the yield and purity of the desired product.
反応中、アルカリとともに添加される水または
反応により生成した水は、反応系から共沸などの
方法で除去することによりエステルの加水分解に
よる副反応を抑制するのがよい。 During the reaction, water added together with the alkali or water produced by the reaction is preferably removed from the reaction system by a method such as azeotropy to suppress side reactions caused by hydrolysis of the ester.
反応終了後、たとえば減圧留去などの操作によ
り反応系内から過剰のエピハロヒドリンを除去す
る。ついでえられた残留物に適当な溶媒を添加し
溶解せしめて副生塩を濾過分離した後、該添加溶
媒を留去して目的物とすることができる。 After the reaction is completed, excess epihalohydrin is removed from the reaction system by, for example, distillation under reduced pressure. Subsequently, an appropriate solvent is added to the resulting residue to dissolve it, the by-product salt is filtered and separated, and the added solvent is distilled off to obtain the desired product.
以下、実施例および比較例をあげて本発明の製
造方法をさらに詳細に説明するが、本発明はかか
る実施例のみに限定されるものではない。 Hereinafter, the manufacturing method of the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
実施例 1
不均化ロジン(酸価160.5mgKOH/g)300g
とトリメチルアミン塩酸塩0.6gをエピクロルヒ
ドリン600gに加え、80℃に加熱し、3時間保温
した。ハロヒドリンエステルが生成し、未反応ロ
ジンがなくなつたことをHLC測定法(カラム:
ODS(山村化学研究所製、YMC Pack A−312、
商品名)、溶媒:メチルアルコール/0.01重量%
リン酸=9/1(容量比)、流速1ml/min、検出
器:示差屈折計(日本ウオーターズリミテツド製
410、品番)により確認した後、120℃に昇温し
水酸化ナトリウム40gを1時間かけて5回に分け
て添加した。この間、生成した水はエピクロルヒ
ドリンと共沸させて除いた。つぎにエピクロルヒ
ドリンを減圧下に留去し、さらに30mmHg、125℃
の条件下に、30分間保持した。残渣にトルエン
400mlを加え、生じた塩化ナトリウムの沈殿を濾
過した。減圧下に濾液よりトルエンを留去し、さ
らに30mmHg、135℃にて、5分間保持した後、不
均化ロジングリシジルエステル330gをえた(収
率:92.7%、純度:82.6%)。このものは淡褐色
粘調な液体でありエポキシ当量は431であつた。Example 1 Disproportionated rosin (acid value 160.5mgKOH/g) 300g
and 0.6 g of trimethylamine hydrochloride were added to 600 g of epichlorohydrin, heated to 80°C, and kept warm for 3 hours. HLC measurement method (column:
ODS (manufactured by Yamamura Chemical Research Institute, YMC Pack A-312,
Product name), Solvent: Methyl alcohol/0.01% by weight
Phosphoric acid = 9/1 (volume ratio), flow rate 1 ml/min, detector: differential refractometer (manufactured by Nippon Waters Limited)
410, product number), the temperature was raised to 120°C, and 40 g of sodium hydroxide was added in 5 portions over 1 hour. During this time, the water produced was removed by azeotroping with epichlorohydrin. Next, epichlorohydrin was distilled off under reduced pressure, and further heated at 30 mmHg and 125°C.
It was held for 30 minutes under these conditions. Toluene in the residue
400 ml was added and the resulting sodium chloride precipitate was filtered. Toluene was distilled off from the filtrate under reduced pressure, and the mixture was maintained at 30 mmHg and 135° C. for 5 minutes to obtain 330 g of disproportionated rosin glycidyl ester (yield: 92.7%, purity: 82.6%). This product was a pale brown viscous liquid with an epoxy equivalent weight of 431.
実施例 2
トリメチルアミン塩酸塩0.6gのかわりにジメ
チルアミン塩酸塩0.9gを用いたほかは実施例1
と同様の操作を行ない、不均化ロジングリシジル
エステル337gをえた(収率:95.0%、純度:
80.4%)。このものは淡褐色粘調な液体でありエ
ポキシ当量は443であつた。Example 2 Example 1 except that 0.9 g of dimethylamine hydrochloride was used instead of 0.6 g of trimethylamine hydrochloride.
The same operation as above was carried out to obtain 337 g of disproportionated rosin glycidyl ester (yield: 95.0%, purity:
80.4%). This product was a light brown viscous liquid and had an epoxy equivalent of 443.
実施例 3
トリメチルアミン塩酸塩0.6gのかわりに塩化
トリメチルベンジルアンモニウム0.6gを用いた
ほかは実施例1と同様の操作を行ない、ガムロジ
ングリシジルエステル337gをえた(収率:94.7
%、純度:80.4%)。このものは淡褐色粘調な液
体でありエポキシ当量は443であつた。Example 3 The same operation as in Example 1 was performed except that 0.6 g of trimethylbenzylammonium chloride was used instead of 0.6 g of trimethylamine hydrochloride, and 337 g of gum rosin glycidyl ester was obtained (yield: 94.7
%, purity: 80.4%). This product was a light brown viscous liquid and had an epoxy equivalent of 443.
実施例 4
不均化ロジン(酸価160.5mgKOH/g)300g
のかわりにガムロジン(酸価168mgKOH/g)
300g、トリメチルアミン塩酸塩0.6gのかわりに
ジメチルアミン塩酸塩0.3gを用いたほかは実施
例1と同様の操作を行ないガムロジングリシジル
エステル338gをえた(収率:94.7%、純度:
82.8%)。このものは淡褐色粘調な液体でありエ
ポキシ当量は430であつた。Example 4 Disproportionated rosin (acid value 160.5mgKOH/g) 300g
Gum rosin instead (acid value 168mgKOH/g)
The same procedure as in Example 1 was performed except that 0.3 g of dimethylamine hydrochloride was used instead of 0.6 g of trimethylamine hydrochloride to obtain 338 g of gum rosin glycidyl ester (yield: 94.7%, purity:
82.8%). This product was a pale brown viscous liquid with an epoxy equivalent of 430.
実施例 5
不均化ロジン(酸価160.5mgKOH/g)300g
のかわりにトール油ロジン(酸価172mgKOH/
g)300gを用いたほかは実施例1と同様の操作
を行ない、トール油ロジングリシジルエステル
343gをえた(収率:96.3%、純度:85.4%)。こ
のものは淡褐色粘調な液体でありエポキシ当量は
417であつた。Example 5 Disproportionated rosin (acid value 160.5mgKOH/g) 300g
Instead, use tall oil rosin (acid value 172mgKOH/
g) Perform the same operation as in Example 1 except that 300 g of tall oil rosin glycidyl ester was used.
343g was obtained (yield: 96.3%, purity: 85.4%). This is a light brown viscous liquid with an epoxy equivalent of
It was 417.
比較例 1
不均化ロジン(酸価160.5mgKOH/g)300g
をエピクロルヒドリン600gに加え、80℃に加熱
して溶解した。トリメチルアミン塩酸塩0.6gと
水酸化ナトリウム40gを同時に加え、80℃で、3
時間保温した。その後、加温しこの間、生成した
水はエピクロルヒドリンと共沸させて除き、さら
に2時間保温した。残渣にトルエン400mlを加え、
塩化ナトリウムの沈殿を濾過した。減圧下に濾液
よりトルエンを溜去し、さらに30mmHg、135℃に
て、5分間保持した後、不均化ロジングリシジル
エステル325gをえた(収率:91.2%、純度:
59.1%)。このものは淡褐色粘調な液体でありエ
ポキシ当量は602であつた。Comparative example 1 Disproportionated rosin (acid value 160.5mgKOH/g) 300g
was added to 600 g of epichlorohydrin and heated to 80°C to dissolve. Add 0.6 g of trimethylamine hydrochloride and 40 g of sodium hydroxide at the same time, and mix at 80°C.
It was kept warm for hours. Thereafter, the mixture was heated, and the water produced during this period was removed by azeotroping with epichlorohydrin, and the mixture was kept warm for an additional 2 hours. Add 400ml of toluene to the residue,
The sodium chloride precipitate was filtered. Toluene was distilled off from the filtrate under reduced pressure and held at 30 mmHg and 135°C for 5 minutes to obtain 325 g of disproportionated rosin glycidyl ester (yield: 91.2%, purity:
59.1%). This product was a pale brown viscous liquid with an epoxy equivalent of 602.
[発明の効果]
本発明の製造方法によれば、ロジングリシジル
エステルを常圧下でしかも高収率かつ高純度で製
造することができる。[Effects of the Invention] According to the production method of the present invention, rosin glycidyl ester can be produced in high yield and purity under normal pressure.
Claims (1)
下に反応させてロジンエピハロヒドリンエステル
とし、ついでアルカリにより脱ハロゲン化水素す
ることを特徴とするロジングリシジルエステルの
製造方法。1. A method for producing a rosin glycidyl ester, which comprises reacting rosin and epihalohydrin in the presence of an amine salt to obtain a rosin epihalohydrin ester, and then dehydrohalogenating with an alkali.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22812187A JPS6469680A (en) | 1987-09-10 | 1987-09-10 | Production of rosin glycidyl ester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22812187A JPS6469680A (en) | 1987-09-10 | 1987-09-10 | Production of rosin glycidyl ester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6469680A JPS6469680A (en) | 1989-03-15 |
JPH0515751B2 true JPH0515751B2 (en) | 1993-03-02 |
Family
ID=16871541
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP22812187A Granted JPS6469680A (en) | 1987-09-10 | 1987-09-10 | Production of rosin glycidyl ester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6469680A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005255904A (en) * | 2004-03-12 | 2005-09-22 | Arakawa Chem Ind Co Ltd | One-pack room temperature curable coating material composition |
WO2024052332A1 (en) | 2022-09-08 | 2024-03-14 | Lamberti Spa | Novel surfactants derived from glycidyl esters of rosin acids |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03115480A (en) * | 1989-09-29 | 1991-05-16 | Arakawa Chem Ind Co Ltd | Manufacture of colorless glycidyl ester of rosin |
JP6194738B2 (en) * | 2012-11-30 | 2017-09-13 | 荒川化学工業株式会社 | Polymerized rosin glycidyl ester and process for producing the same |
JP6202470B2 (en) * | 2012-12-13 | 2017-09-27 | 荒川化学工業株式会社 | Polymerized rosin-based epoxy composition, method for producing the same, and curable epoxy resin composition |
JP6103476B2 (en) * | 2013-02-15 | 2017-03-29 | 荒川化学工業株式会社 | Curable composition for sealing electronic parts and cured product thereof |
-
1987
- 1987-09-10 JP JP22812187A patent/JPS6469680A/en active Granted
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005255904A (en) * | 2004-03-12 | 2005-09-22 | Arakawa Chem Ind Co Ltd | One-pack room temperature curable coating material composition |
JP4605534B2 (en) * | 2004-03-12 | 2011-01-05 | 荒川化学工業株式会社 | 1-pack room temperature curable coating composition |
WO2024052332A1 (en) | 2022-09-08 | 2024-03-14 | Lamberti Spa | Novel surfactants derived from glycidyl esters of rosin acids |
Also Published As
Publication number | Publication date |
---|---|
JPS6469680A (en) | 1989-03-15 |
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