JPH0959570A - Rosin derivative and its production - Google Patents
Rosin derivative and its productionInfo
- Publication number
- JPH0959570A JPH0959570A JP23767095A JP23767095A JPH0959570A JP H0959570 A JPH0959570 A JP H0959570A JP 23767095 A JP23767095 A JP 23767095A JP 23767095 A JP23767095 A JP 23767095A JP H0959570 A JPH0959570 A JP H0959570A
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- acid
- carboxyl group
- rosin derivative
- derivative
- 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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 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 title claims abstract description 73
- 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 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 15
- FEPCMSPFPMPWJK-OLPJDRRASA-N maleopimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]3C(OC(=O)[C@@H]23)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O FEPCMSPFPMPWJK-OLPJDRRASA-N 0.000 claims abstract description 12
- PXYRCOIAFZBLBN-HQJFNQTASA-N fumaropimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]([C@@H]2C(O)=O)C(O)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O PXYRCOIAFZBLBN-HQJFNQTASA-N 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003995 emulsifying agent Substances 0.000 abstract description 2
- 230000004907 flux Effects 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract description 2
- 238000005476 soldering Methods 0.000 abstract description 2
- 239000003784 tall oil Substances 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- 229920003002 synthetic resin Polymers 0.000 abstract 1
- 239000000057 synthetic resin Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 4
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 4
- 229940118781 dehydroabietic acid Drugs 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RWWVEQKPFPXLGL-ONCXSQPRSA-N L-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC=C(C(C)C)C=C2CC1 RWWVEQKPFPXLGL-ONCXSQPRSA-N 0.000 description 2
- RWWVEQKPFPXLGL-UHFFFAOYSA-N Levopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CC=C(C(C)C)C=C1CC2 RWWVEQKPFPXLGL-UHFFFAOYSA-N 0.000 description 2
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 2
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YPGLTKHJEQHKSS-ASZLNGMRSA-N (1r,4ar,4bs,7r,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-1-carboxylic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@H](C(C)C)C[C@@H]2CC1 YPGLTKHJEQHKSS-ASZLNGMRSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UZZYXZWSOWQPIS-UHFFFAOYSA-N 3-fluoro-5-(trifluoromethyl)benzaldehyde Chemical compound FC1=CC(C=O)=CC(C(F)(F)F)=C1 UZZYXZWSOWQPIS-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、第１級カルボキシ
ル基を含有してなる新規なロジン誘導体およびその製造
方法に関する。本発明のロジン誘導体は、従来よりロジ
ンが使用されてきたサイズ剤、粘着付与剤、印刷イン
キ、道路標示材、合成ゴムの乳化剤、半田付けフラック
ス等の各種の用途に利用できる。TECHNICAL FIELD The present invention relates to a novel rosin derivative containing a primary carboxyl group and a method for producing the same. INDUSTRIAL APPLICABILITY The rosin derivative of the present invention can be used in various applications such as sizing agents, tackifiers, printing inks, road marking materials, emulsifiers for synthetic rubber, soldering flux, etc., for which rosin has been used conventionally.
【０００２】[0002]
【従来の技術】ロジンは、アビエチン酸、ネオアビエチ
ン酸、パラストリン酸、レボピマール酸等を有効成分と
してなり、崇高いヒドロフェナンスレン骨格の第３級炭
素にカルボキシル基が結合する化学構造を有する。その
ため、ロジンの含有するカルボキシル基の活性は、その
立体障害や、カルボキシル基の結合炭素ゆえに一般に弱
い。2. Description of the Related Art Rosin contains abietic acid, neoabietic acid, parastophosphoric acid, levopimaric acid and the like as active ingredients, and has a chemical structure in which a carboxyl group is bonded to the tertiary carbon of the sublime hydrophenanthrene skeleton. Therefore, the activity of the carboxyl group contained in the rosin is generally weak due to the steric hindrance and the bonding carbon of the carboxyl group.
【０００３】また、ロジンの共役ジエン樹脂酸成分と、
マレイン酸やアクリル酸等を付加反応（ディールス・ア
ルダー反応）させて得られるマレオピマール酸やアクリ
ロピマール酸等のロジン誘導体も知られている。かかる
ロジン誘導体のカルボキシル基は、第２級カルボキシル
基を含み、また立体障害が幾分少なくなる。しかし、カ
ルボキシル基の活性は十分とはいえない。Further, a conjugated diene resin acid component of rosin,
Rosin derivatives such as maleopimaric acid and acrylopimaric acid obtained by addition reaction (Diels-Alder reaction) of maleic acid and acrylic acid are also known. The carboxyl groups of such rosin derivatives contain secondary carboxyl groups and are somewhat less sterically hindered. However, the activity of the carboxyl group is not sufficient.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、ロジンに第
１級カルボキシル基を導入することにより、活性の高い
新規なロジン誘導体を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel rosin derivative having high activity by introducing a primary carboxyl group into rosin.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、第１級カ
ルボキシル基を含有してなる新規なロジン誘導体を提供
すべく鋭意検討を重ねた結果、下記の新規なロジン誘導
体を導き出すに至った。Means for Solving the Problems The present inventors have conducted extensive studies to provide a novel rosin derivative containing a primary carboxyl group, and as a result, have derived the following novel rosin derivative. It was
【０００６】すなわち、本発明は、一般式（１）：Ｒ
−ＣＯＯ−（ＣＨ2 ＣＯＯ）n −Ｈ（式中、Ｒはロジン
残基、ｎは１〜５を表す）で表されるロジン誘導体、
ロジン類と、グリコール酸とを反応させて得られる第１
級カルボキシル基含有ロジン誘導体、ロジン類と、グ
リコール酸とを反応させることを特徴とする第１級カル
ボキシル基含有ロジン誘導体の製造方法、マレオピマ
ール酸、フマロピマール酸およびアクリロピマール酸か
ら選ばれるいずれか少なくとも１種と、グリコール酸と
を反応させて得られる第１級カルボキシル基含有ロジン
誘導体、並びにマレオピマール酸、フマロピマール酸
およびアクリロピマール酸から選ばれるいずれか少なく
とも１種と、グリコール酸とを反応させることを特徴と
する第１級カルボキシル基含有ロジン誘導体の製造方法
に関する。That is, the present invention is based on the general formula (1): R
A rosin derivative represented by —COO— (CH 2 COO) n —H (wherein R represents a rosin residue and n represents 1 to 5);
First obtained by reacting rosins with glycolic acid
Primary carboxyl group-containing rosin derivative, a method for producing a primary carboxyl group-containing rosin derivative, which comprises reacting rosin with glycolic acid, and at least one selected from maleopimaric acid, fumaropimaric acid and acrylopimaric acid And a glycolic acid are reacted with a primary carboxyl group-containing rosin derivative obtained by reacting carboxylic acid with glycolic acid, and with at least one selected from maleopimaric acid, fumaropimaric acid and acrylopimaric acid. The present invention relates to a method for producing a primary carboxyl group-containing rosin derivative.
【０００７】本発明の第１級カルボキシル基を含有して
なるロジン誘導体は、ロジン類と、グリコール酸を反応
させることにより製造される。なお、グリコール酸は市
販されている結晶または水溶液のいずれの形態でも使用
できる。The rosin derivative containing a primary carboxyl group of the present invention is produced by reacting rosin with glycolic acid. Glycolic acid can be used in the form of either a commercially available crystal or an aqueous solution.
【０００８】ロジン類としては、ガムロジン、トール油
ロジン、ウッドロジン等の原料ロジン類、当該原料ロジ
ン類に蒸留工程、水添工程および不均化工程のいずれか
少なくとも１つの工程を施して得られる各種の変性ロジ
ン類（蒸留ロジン、水添ロジン、不均化ロジン等や、い
わゆる無色ロジン）や、重合ロジン等があげられる。な
お、これらロジン類は、アビエチン酸、ネオアビエチン
酸、パラストリン酸、レボピマール酸、デヒドロアビエ
チン酸、ジヒドロアビエチン酸、テトラヒドロアビエチ
ン酸等の各種の化合物を有効成分として含有するが、本
発明のロジン類は、これら化合物の混合物であってもよ
い。The rosins include raw rosins such as gum rosin, tall oil rosin and wood rosin, and various rosins obtained by subjecting the raw rosins to at least one of a distillation step, a hydrogenation step and a disproportionation step. Rosins (distilled rosin, hydrogenated rosin, disproportionated rosin, and so-called colorless rosin), and polymerized rosin. These rosins contain various compounds such as abietic acid, neoabietic acid, parastolic acid, levopimaric acid, dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid as active ingredients. Or a mixture of these compounds.
【０００９】かかるロジン類と、グリコール酸との反応
は、公知のエステル化反応と同様に行うことができる。
グリコール酸の使用量は、ロジン類のカルボキシル基１
当量に対して、グリコール酸のヒドロキシ基が０．２〜
１０当量、好ましくは０．３〜５当量である。グリコー
ル酸の使用量が０．２当量より少ない場合には、ロジン
誘導体に導入される第１級カルボキシル基の割合が少な
く、得られるロジン誘導体に十分な活性を付与し難く、
また１０当量を越える場合には、グリコール酸によりロ
ジン類の分解が促進されるため、得られる第１級カルボ
キシル基含有ロジン誘導体の収率が低下するばかりでな
く色調が低下するため、いずれの場合も好ましくない。The reaction of such rosins with glycolic acid can be carried out in the same manner as the known esterification reaction.
The amount of glycolic acid used is the carboxyl group 1 of rosins.
The hydroxy group of glycolic acid is 0.2 to
It is 10 equivalents, preferably 0.3 to 5 equivalents. When the amount of glycolic acid used is less than 0.2 equivalents, the proportion of primary carboxyl groups introduced into the rosin derivative is small, and it is difficult to impart sufficient activity to the obtained rosin derivative.
On the other hand, when the amount exceeds 10 equivalents, glycolic acid accelerates the decomposition of rosins, which not only lowers the yield of the obtained primary carboxyl group-containing rosin derivative but also lowers the color tone. Is also not preferable.
【００１０】エステル化の反応温度は、通常、２００〜
３００℃程度、好ましくは２３０〜２８０℃程度であ
り、反応時間は１０分〜４時間程度、好ましくは１５分
〜２時間程度である。また、エステル化反応は、通常、
窒素雰囲気下に、生成する水を除去しながら行う。The reaction temperature for esterification is usually 200 to
The reaction temperature is about 300 ° C, preferably about 230 to 280 ° C, and the reaction time is about 10 minutes to 4 hours, preferably about 15 minutes to 2 hours. Further, the esterification reaction is usually
This is performed in a nitrogen atmosphere while removing generated water.
【００１１】なお、エステル化反応に際しては、エステ
ル化触媒として塩酸、硫酸等の鉱酸、芳香族スルホン酸
等の有機酸、フッ化ホウ素エーテル、塩化アルミニウム
等のルイス酸や、酸化亜鉛、水酸化カルシウム等の、一
般的なエステル化触媒を使用することもできる。In the esterification reaction, mineral acids such as hydrochloric acid and sulfuric acid, organic acids such as aromatic sulfonic acid, Lewis acids such as boron fluoride ether and aluminum chloride, zinc oxide, and hydroxide are used as esterification catalysts. Common esterification catalysts such as calcium can also be used.
【００１２】かくして得られた第１級カルボキシル基含
有ロジン誘導体は、通常、一般式（１）においてｎ＝１
〜５のロジン誘導体を含有する混合物として得られる。
また、反応生成物中には、未反応のロジン類を含んでい
てもよい。こうした反応生成物は、減圧蒸留や、カラム
分取により、一般式（１）においてｎ＝１〜５のそれぞ
れのロジン誘導体に分離される。The primary carboxyl group-containing rosin derivative thus obtained is generally represented by n = 1 in the general formula (1).
Obtained as a mixture containing -5 rosin derivatives.
Moreover, the reaction product may contain unreacted rosins. Such a reaction product is separated into each rosin derivative of n = 1 to 5 in the general formula (1) by vacuum distillation or column fractionation.
【００１３】また、本発明における第１級カルボキシル
基を含有してなるロジン誘導体は、マレオピマール酸、
フマロピマール酸およびアクリロピマール酸から選ばれ
るいずれか少なくとも１種と、グリコール酸を反応させ
ることにより製造することもできる。The rosin derivative containing a primary carboxyl group in the present invention is maleopimaric acid,
It can also be produced by reacting at least one selected from fumaropimaric acid and acrylopimaric acid with glycolic acid.
【００１４】マレオピマール酸、フマロピマール酸また
はアクリロピマール酸は、前記原料ロジン類の共役ジエ
ン樹脂酸成分と、マレイン酸、フマル酸またはアクリル
酸とを付加反応（ディールス・アルダー反応）させて得
られるものであり、これらマレオピマール酸等は必ずし
も精製したものを使用する必要はなく、未反応の原料ロ
ジン類を含有する反応生成物を使用することもできる。
なお、マレオピマール酸等とグリコール酸との反応は、
前記ロジン類とグリコール酸とのエステル化反応と同様
の条件下に行うことができる。Maleopimaric acid, fumaropimaric acid or acrylopimaric acid is obtained by an addition reaction (Diels-Alder reaction) between the conjugated diene resin acid component of the raw material rosin and maleic acid, fumaric acid or acrylic acid. However, it is not always necessary to use a purified one of these maleopimaric acid and the like, and a reaction product containing unreacted raw material rosin can also be used.
The reaction between maleopimaric acid and glycolic acid is
It can be carried out under the same conditions as the esterification reaction of the rosins with glycolic acid.
【００１５】かくして得られた第１級カルボキシル基含
有ロジン誘導体は、マレオピマール酸、フマロピマール
酸またはアクリロピマール酸の第３級炭素および／また
は第２級炭素に結合したカルボキシル基１当量に、グリ
コール酸が１〜５当量程度付加したエステル化物の混合
物であり、反応生成物中には、未反応の原料ロジン類
や、マレオピマール酸、フマロピマール酸、アクリロピ
マール酸等を含んでいてもよい。The thus-obtained primary carboxyl group-containing rosin derivative has 1 equivalent of the carboxyl group bonded to the tertiary carbon and / or the secondary carbon of maleopimaric acid, fumaropimaric acid or acrylopimaric acid, and 1 mol of glycolic acid. The reaction product may contain unreacted raw material rosin, maleopimaric acid, fumaropimaric acid, acrylopimaric acid, etc.
【００１６】なお、本発明で得られた第１級カルボキシ
ル基を含有してなるロジン誘導体は、一般式（１）で表
されるロジン誘導体のように反応生成物から分離した後
に、従来よりロジンが使用されてきた各種の用途に使用
できる他、未反応のロジン類等を含む反応生成物を、そ
のまま各種の用途に同様に使用できる。The rosin derivative containing a primary carboxyl group obtained in the present invention is separated from the reaction product like the rosin derivative represented by the general formula (1), and then the rosin derivative is conventionally used. In addition to being used for various uses that have been used, the reaction product containing unreacted rosin and the like can be used as it is for various uses.
【００１７】[0017]
【実施例】以下に、実施例をあげて本発明を詳細に説明
するが、本発明はかかる実施例に限られるものではな
い。The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
【００１８】[0018]
実施例１（ロジン類とグリコール酸との反応生成物） 分水管を備えた３００ｍｌ容の４ツ口フラスコに、デヒ
ドロアビエチン酸１５０ｇを仕込み、窒素雰囲気下で加
熱撹拌しながら、１５０℃に昇温し、溶融させた。次い
で、グリコール酸３５ｇを仕込んだ。加熱する一方で反
応水を除去しながら、２８０℃まで昇温して保持した。
１時間経過後、ＧＰＣ（ゲル浸透クロマトグラフィー）
により、グリコール酸がなくなったのを確認した後、１
０ｍｍＨｇで減圧蒸留を行い、残留している水とロジン
分解物を除去し、第１級カルボキシル基含有ロジン誘導
体を得た。Example 1 (Reaction product of rosin and glycolic acid) A 300-ml four-necked flask equipped with a water diversion tube was charged with 150 g of dehydroabietic acid, and heated to 150 ° C. with heating and stirring under a nitrogen atmosphere. And melted. Next, 35 g of glycolic acid was charged. While heating, the reaction water was removed and the temperature was raised to and maintained at 280 ° C.
After 1 hour, GPC (gel permeation chromatography)
After confirming that the glycolic acid is gone,
Distillation under reduced pressure was performed at 0 mmHg to remove residual water and rosin decomposition products to obtain a primary carboxyl group-containing rosin derivative.
【００１９】得られた第１級カルボキシル基含有ロジン
誘導体から、シリカゲルカラム分取により、一般式
（１）においてｎ＝１のデヒドロアビエチン酸型のロジ
ン誘導体のみを分離した。得られたデヒドロアビエチン
酸型のロジン誘導体の 1Ｈ−ＮＭＲチャート（３００Ｍ
Ｈｚ，ＣＤＣｌ3 ）、13Ｃ−ＮＭＲチャート（３００Ｍ
Ｈｚ，ＣＤＣｌ3 ）、ＩＲチャート（ｎｅａｔ，ＣＣｌ
4 ）、ＧＰＣチャート（測定機器：ＨＬＣ−８０２０
（東ソー（株）製，カラム名：ＴＳＫ ｇｅｌ Ｇ２０
００ＨＸＬ、２本，溶媒：テトラヒドロフラン，検出方
法：ＲＩ検出）を図１〜４に示す。From the obtained primary carboxyl group-containing rosin derivative, only the dehydroabietic acid type rosin derivative of the general formula (1) where n = 1 was separated by silica gel column fractionation. 1 H-NMR chart (300 M of the obtained dehydroabietic acid type rosin derivative
Hz, CDCl 3 ), 13 C-NMR chart (300M
Hz, CDCl 3 ), IR chart (neat, CCl
4 ), GPC chart (measuring instrument: HLC-8020
(Tosoh Corporation, column name: TSK gel G20
00HXL, 2 pieces, solvent: tetrahydrofuran, detection method: RI detection) are shown in FIGS.
【００２０】実施例２（アクリロピマール酸とグリコー
ル酸との反応生成物） 分水管を備えた３００ｍｌ容の４ツ口フラスコに、アク
リロピマール酸１００ｇを仕込み、窒素雰囲気下で加熱
撹拌しながら、１８０℃に昇温し、溶融させた。次い
で、グリコール酸２０ｇを仕込んだ。加熱する一方で反
応水を除去しながら、２５０℃まで昇温して保持した。
１時間経過後、ＧＰＣ（ゲル浸透クロマトグラフィー）
により、グリコール酸がなくなったのを確認した後、３
０ｍｍＨｇで減圧蒸留を行い、残留している水とロジン
分解物を除去し、第１級カルボキシル基含有ロジン誘導
体を得た。得られた第１級カルボキシル基含有ロジン誘
導体のＩＲチャート（ｎｅａｔ，ＣＣｌ4 ）を図５に示
す。Example 2 (Reaction product of acrylopimaric acid and glycolic acid) A 300 ml four-necked flask equipped with a water diversion tube was charged with 100 g of acrylopimaric acid, and heated to 180 ° C. under stirring under a nitrogen atmosphere. The temperature was raised and melted. Next, 20 g of glycolic acid was charged. The temperature was raised to and held at 250 ° C. while removing the reaction water while heating.
After 1 hour, GPC (gel permeation chromatography)
After confirming that the glycolic acid is gone,
Distillation under reduced pressure was performed at 0 mmHg to remove residual water and rosin decomposition products to obtain a primary carboxyl group-containing rosin derivative. An IR chart (neat, CCl 4 ) of the obtained primary carboxyl group-containing rosin derivative is shown in FIG.
【図１】実施例１で得られたロジン誘導体の 1Ｈ−ＮＭ
Ｒチャートである。FIG. 1 1 H-NM of rosin derivative obtained in Example 1.
It is an R chart.
【図２】実施例１で得られたロジン誘導体の13Ｃ−ＮＭ
Ｒチャートである。[2] 13 C-NM rosin derivatives obtained in Example 1
It is an R chart.
【図３】実施例１で得られたロジン誘導体のＩＲチャー
トである。FIG. 3 is an IR chart of the rosin derivative obtained in Example 1.
【図４】実施例１で得られたロジン誘導体のＧＰＣチャ
ートである。FIG. 4 is a GPC chart of the rosin derivative obtained in Example 1.
【図５】実施例２で得られたロジン誘導体のＩＲチャー
トである。5 is an IR chart of the rosin derivative obtained in Example 2. FIG.
Claims (5)
ＯＯ）n −Ｈ（式中、Ｒはロジン類残基、ｎは１〜５の
整数を表す）で表されるロジン誘導体。1. General formula (1): R—COO— (CH 2 C
OO) n -H (wherein R represents a rosin residue and n represents an integer of 1 to 5).
て得られる第１級カルボキシル基含有ロジン誘導体。2. A primary carboxyl group-containing rosin derivative obtained by reacting rosins with glycolic acid.
ることを特徴とする第１級カルボキシル基含有ロジン誘
導体の製造方法。3. A method for producing a primary carboxyl group-containing rosin derivative, which comprises reacting rosin with glycolic acid.
よびアクリロピマール酸から選ばれるいずれか少なくと
も１種と、グリコール酸とを反応させて得られる第１級
カルボキシル基含有ロジン誘導体。4. A primary carboxyl group-containing rosin derivative obtained by reacting at least one selected from maleopimaric acid, fumaropimaric acid and acrylopimaric acid with glycolic acid.
よびアクリロピマール酸から選ばれるいずれか少なくと
も１種と、グリコール酸とを反応させることを特徴とす
る第１級カルボキシル基含有ロジン誘導体の製造方法。5. A method for producing a primary carboxyl group-containing rosin derivative, which comprises reacting at least one selected from maleopimaric acid, fumaropimaric acid and acrylopimaric acid with glycolic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7237670A JP2980009B2 (en) | 1995-08-22 | 1995-08-22 | Rosin derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7237670A JP2980009B2 (en) | 1995-08-22 | 1995-08-22 | Rosin derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0959570A true JPH0959570A (en) | 1997-03-04 |
| JP2980009B2 JP2980009B2 (en) | 1999-11-22 |
Family
ID=17018774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7237670A Expired - Lifetime JP2980009B2 (en) | 1995-08-22 | 1995-08-22 | Rosin derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2980009B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0970689A (en) * | 1995-09-05 | 1997-03-18 | Arakawa Chem Ind Co Ltd | Flux composition for soldering and cream solder composition |
| JPH10233577A (en) * | 1997-02-20 | 1998-09-02 | Taiho Kogyo Co Ltd | Solder paste |
| JP2009084421A (en) * | 2007-09-28 | 2009-04-23 | Arakawa Chem Ind Co Ltd | Tackifier, tackifier for medical patch, adhesive or adhesive composition, and adhesive for medical patch |
| CN110627947A (en) * | 2019-10-30 | 2019-12-31 | 广西民族大学 | A kind of highly cross-linked rosin-based polymer microspheres and its preparation method and application |
| US20200239412A1 (en) * | 2017-09-29 | 2020-07-30 | Fredrik Elinder | New derivates of dhaa with electrostatic tuning |
| CN115920868A (en) * | 2022-09-30 | 2023-04-07 | 广西民族大学 | Modified maleopimaric acid bonded silica gel chromatographic stationary phase and preparation method and application thereof |
-
1995
- 1995-08-22 JP JP7237670A patent/JP2980009B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0970689A (en) * | 1995-09-05 | 1997-03-18 | Arakawa Chem Ind Co Ltd | Flux composition for soldering and cream solder composition |
| JPH10233577A (en) * | 1997-02-20 | 1998-09-02 | Taiho Kogyo Co Ltd | Solder paste |
| JP2009084421A (en) * | 2007-09-28 | 2009-04-23 | Arakawa Chem Ind Co Ltd | Tackifier, tackifier for medical patch, adhesive or adhesive composition, and adhesive for medical patch |
| US20200239412A1 (en) * | 2017-09-29 | 2020-07-30 | Fredrik Elinder | New derivates of dhaa with electrostatic tuning |
| CN110627947A (en) * | 2019-10-30 | 2019-12-31 | 广西民族大学 | A kind of highly cross-linked rosin-based polymer microspheres and its preparation method and application |
| CN115920868A (en) * | 2022-09-30 | 2023-04-07 | 广西民族大学 | Modified maleopimaric acid bonded silica gel chromatographic stationary phase and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2980009B2 (en) | 1999-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5395920A (en) | Process for preparing rosin and colorless rosin comprising disproportionation and dehydrogenation | |
| US4847010A (en) | Process for preparing rosin ester with esterification and hydrogenation | |
| EP0653471B1 (en) | Process for producing colorless rosin | |
| JP2666651B2 (en) | Colorless rosin derivative and production method thereof | |
| JP7503374B2 (en) | Light-colored rosin and rosin ester compositions | |
| JP2980009B2 (en) | Rosin derivative and method for producing the same | |
| EP0270773B1 (en) | Method of preparing rosin esters of improved thermal stability | |
| EP0270774B1 (en) | Improved process of preparing polyol esters of rosin | |
| US4693847A (en) | Method of preparing hot-melt stable rosin ester with organic ester of hypophosphorous acid catalyst | |
| JPH0224291B2 (en) | ||
| US4906733A (en) | Process for preparing colorless rosin | |
| JP2953187B2 (en) | Method for producing colorless rosin | |
| JP2539851B2 (en) | Method for producing colorless rosin | |
| JP2795018B2 (en) | Rosin ester production method | |
| JP3371972B2 (en) | Rosin ester production method | |
| JPH10230388A (en) | Cream solder using fine powder solder | |
| JPH0586333A (en) | Colorless rosin ester derivative and its production | |
| US2511603A (en) | Resin acid nitrile | |
| Bei et al. | The Synthesis and Properties of New Oxygen-and Nitrogen-Containing Terpene Acid Derivatives | |
| JP3405865B2 (en) | Flux composition for soldering and cream solder composition | |
| JPH10233577A (en) | Solder paste | |
| US3658891A (en) | Method for synthesizing maleopimaric acid | |
| JPH05271621A (en) | Production of colorless rosin | |
| JP2017066093A (en) | Dinitrile compound and method for producing the same | |
| US1829480A (en) | Organic ester and process of making the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080917 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090917 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090917 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090917 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100917 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100917 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110917 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110917 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120917 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120917 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120917 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130917 Year of fee payment: 14 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |