CN1235180A - Rosin catalyzed by rare-earth metal oxide and method of esterification of derivatives thereof - Google Patents
Rosin catalyzed by rare-earth metal oxide and method of esterification of derivatives thereof Download PDFInfo
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- CN1235180A CN1235180A CN 99116159 CN99116159A CN1235180A CN 1235180 A CN1235180 A CN 1235180A CN 99116159 CN99116159 CN 99116159 CN 99116159 A CN99116159 A CN 99116159A CN 1235180 A CN1235180 A CN 1235180A
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- Prior art keywords
- rosin
- derivatives
- rare
- alcohol
- esterification
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- 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 27
- 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 27
- 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 27
- 238000000034 method Methods 0.000 title claims abstract description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 title claims description 17
- 230000032050 esterification Effects 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 4
- 150000001298 alcohols Chemical class 0.000 claims 3
- 230000035484 reaction time Effects 0.000 abstract description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000376 reactant Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- -1 polyol ester Chemical class 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a process for esterifying rosin and its derivatives under the catalysis of rare-earth metal oxide and dicloses a catalyst. Said catalyst for esterifying rosin and its derivatives is the oxides of three-valence rure-earth metals, especially Nd2O3, Sm2O3, Gd2O3 and La2O3. The advantages of said catalyst include less consumption (0.08-2%), short reaction time, low reaction temp and uniform transparency and light colour of esterified products.
Description
The present invention relates to the novel method of a kind of rosin and esterification of derivatives thereof.
Rosin is the first afforestation product resource of China, as a kind of natural resin of excellent property, has obtained using widely.But rosin is crisp, easy oxidation discoloration, has hindered its application to a certain extent.Esterification modification is to widen one of most important means of fundamental sum of rosin application approach.After the rosin esterification modification, performance is improved greatly.Various rosin (comprising nilox resin and staybelite) ester accounts for more than 60% of Abietyl modified product, and its polyol ester is widely used in industries such as coating, printing ink, rubber, tackiness agent as tackifier; The monobasic alcohol ester also can be used as rubber and plastic processing additives.
The rosin that generally adopts and the esterifying catalyst of derivative thereof have bronsted acid catalyst now, as sulfuric acid, Hypophosporous Acid, 50 etc.; Solid acid catalyst such as zinc oxide.The esterification reaction tech of these catalyst rosin and derivative thereof need high temperature (250～300 ℃) and long-time (7～11h) (" modern chemical industry ", 1994,2, p43), energy consumption of reaction is big, by product is many, as follows easily produces PH during phosphoric acid catalyzed
3Deng toxic gas contaminate environment (US.4690783); Sulfuric acid then easily makes the rosin decarboxylation and reaction vessel is had corrosive nature (US.4172070).The catalytic reaction of protonic acid generally needs in the alkali and aftertreatment (US.4650607) such as grade.
The objective of the invention is for the rosin esterification modified industry provides a kind of novel, highly active catalyzer, rosin and derivatives catalysis esterification thereof are synthesized their ester compound; Its polyol ester is the tackifier of macromolecular material, and the monobasic alcohol ester is the softening agent of macromolecular material.
Rosin esterification catalyzer provided by the present invention, rare-earth oxide is compared with traditional protonic acid, solid acid catalyst, and it is few to have a catalyst levels, the short and low characteristics of temperature of reaction of reaction times; Esterified prod homogeneous transparent, lighter color.From the industrial application angle, unfavorable factors such as such catalyzer has been eliminated traditional protonic acid, the solid acid catalyst activity is not high, side reaction is many, long reaction time, energy consumption height, contaminate environment, thus make the esterification modification process of rosin and derivative thereof can better be fit to the needs of modern chemical industry production development.
The enforcement of rosin and esterification of derivatives method thereof comprises following process: add catalyzer around the rare-earth oxide account for reactant weight 0.08～1.2% (the best is 0.4～1.2%) in rosin or derivatives thereof and the pure reaction system, 200～260 ℃ of temperature of reaction, 2～6 hours reaction times; Boil off remaining alcohol and solvent and can obtain the ester compound of rosin or derivatives thereof.Rosin derivative mainly is to contain carboxy derivatives in the reaction system, and reactant alcohols carbonatoms is 1～18 (the best is 2～12 carbon atoms), comprises monohydroxy-alcohol, dibasic alcohol, trivalent alcohol or the tetravalent alcohol etc. of Fatty Alcohol(C12-C14 and C12-C18) and aromatic alcohol.Catalyzer rare earth metal oxide compound is the trivalent rare earth metals oxide compound of ordination number between 57～71, for example Nd
2O
3, Sm
2O
3, Gd
2O
3, La
2O
3Deng.Rosin derivative is meant as nilox resin, staybelite etc.
Embodiment 1:
Get 0.5 mole of rosin acid, 0.6 mole of isooctyl alcohol, 0.5 gram Nd
2O
3Insert in the four neck round-bottomed flasks that dropping funnel, thermometer, agitator, reflux exchanger and water trap are housed, be heated to reactants dissolved with electric mantle, stir, when treating that temperature rises to 220 ℃, in reaction system, drip an amount of toluene dehydration, control reaction temperature is in about 200 ℃, clock, after 5 hours, theoretical amount has been arrived in water outlet in the water trap; Steam residual toluene and isooctyl alcohol; Stop heating, the system for the treatment of is cooled to about 100 ℃, inclines to reaction product, and transformation efficiency is greater than 95%.Embodiment 2:
Get 0.5 mole of rosin acid, 0.5 gram Sm
2O
3Insert in the four neck round-bottomed flasks that dropping funnel, thermometer, agitator, reflux exchanger and water trap are housed, be heated to reactants dissolved with electric mantle, stir, when treating that temperature rises to 240 ℃, in reaction system, drip the lauryl alcohol of calculated amount, the control rate of addition remains in about 240 ℃ temperature, clock, after 3.5 hours, theoretical amount has been arrived in water outlet in the water trap; Steam remaining lauryl alcohol; Stop heating, the system for the treatment of is cooled to about 100 ℃, inclines to reaction product, and transformation efficiency is greater than 92%.Embodiment 3:
Get 0.6 mole of rosin acid, 0.2 mole of glycerine, 0.5 gram Nd
2O
3, insert in the four neck round-bottomed flasks that dropping funnel, reflux exchanger, thermometer and agitator are housed, be heated to reactants dissolved with electric mantle, stir, control reaction temperature clocks in about 240 ℃, and after 90 minutes, theoretical amount has been arrived in water outlet in the water trap; Steam residual water and glycerine; Stop heating, the system for the treatment of is cooled to about 150 ℃, inclines to reaction product, and transformation efficiency is greater than 98%.Embodiment 4:
Get 0.4 mole of rosin acid, 0.1 mole of tetramethylolmethane, 0.5 gram Nd
2O
3, insert in the four neck round-bottomed flasks that dropping funnel, reflux exchanger, thermometer and agitator are housed, be heated to reactants dissolved with electric mantle, stir, control reaction temperature clocks in about 260 ℃, and behind the 2.5h, theoretical amount has been arrived in water outlet in the water trap; Steam remaining alcohol; Stop heating, the system for the treatment of is cooled to about 150 ℃, inclines to reaction product, and transformation efficiency is greater than 95%.Embodiment 5:
Get 0.5 mole of nilox resin resinous acid, 0.3 mole of glycol ether, 0.5 gram Gd
2O
3Insert in the four neck round-bottomed flasks that dropping funnel, thermometer, agitator, reflux exchanger and water trap are housed, be heated to reactants dissolved with electric mantle, stir, when treating that temperature rises to 240 ℃, in reaction system, drip an amount of toluene dehydration, control reaction temperature is in about 240 ℃, clock, after 4 hours, theoretical amount has been arrived in water outlet in the water trap; Steam residual toluene and glycol ether; Stop heating, the system for the treatment of is cooled to about 100 ℃, inclines to reaction product, and transformation efficiency is greater than 90%.Embodiment 6:
Get 0.5 mole of staybelite resinous acid, 0.6 mole of phenylcarbinol, 0.5 gram La
2O
3Insert in the four neck round-bottomed flasks that dropping funnel, thermometer, agitator, reflux exchanger and water trap are housed, be heated to reactants dissolved with electric mantle, stir, when treating that temperature rises to 200 ℃, in reaction system, drip an amount of toluene dehydration, control reaction temperature is in about 200 ℃, clock, after 90 minutes, theoretical amount has been arrived in water outlet in the water trap; Steam residual toluene and phenylcarbinol; Stop heating, the system for the treatment of is cooled to about 100 ℃, inclines to reaction product, and transformation efficiency is greater than 97%.
Claims (5)
1. rosin and derivatives catalysis esterification method thereof, it is characterized in that adding in the reaction system of rosin or derivatives thereof and alcohols the rare-earth oxide that accounts for rosin or derivatives thereof weight 0.08%～2% and make catalyzer, 200～260 ℃ of temperature of reaction were reacted 2～6 hours.
2. according to the catalytic esterification method described in the claim 1, it is characterized in that described rare-earth oxide is the ordination number rare-earth oxide between 57～71, especially Nd
2O
3, Sm
2O
3, Gd
2O
3, La
2O
3
3. according to the catalytic esterification method described in claim 1 or 2, it is characterized in that it can be 0.4～1.2% of rosin or derivatives thereof weight that described rare-earth oxide is made catalyst consumption.
4. according to the catalytic esterification method described in the claim 1, it is characterized in that the alcohols in the described reaction system, comprise Fatty Alcohol(C12-C14 and C12-C18) and aromatic alcohol, the carbonatoms of alcohols is 1～18, especially is 2～12, monohydroxy-alcohol, dibasic alcohol, trivalent alcohol and tetravalent alcohol.
5. according to the catalytic esterification method described in the claim 1, it is characterized in that this method is applicable to rosin and contains the esterification of carboxy derivatives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116159A CN1074444C (en) | 1999-04-28 | 1999-04-28 | Rosin catalyzed by rare-earth metal oxide and method of esterification of derivatives thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116159A CN1074444C (en) | 1999-04-28 | 1999-04-28 | Rosin catalyzed by rare-earth metal oxide and method of esterification of derivatives thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1235180A true CN1235180A (en) | 1999-11-17 |
| CN1074444C CN1074444C (en) | 2001-11-07 |
Family
ID=5279002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99116159A Expired - Fee Related CN1074444C (en) | 1999-04-28 | 1999-04-28 | Rosin catalyzed by rare-earth metal oxide and method of esterification of derivatives thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1074444C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387667C (en) * | 2006-02-07 | 2008-05-14 | 福州大学 | Rosin-modified resin of high-boiling alcohol lignin or its derivatives and preparation method thereof |
| CN100424146C (en) * | 2002-08-30 | 2008-10-08 | 大日本油墨化学工业株式会社 | Drier for printing ink and printing ink containing the drier |
| CN107573850A (en) * | 2017-09-18 | 2018-01-12 | 广西众昌树脂有限公司 | The preparation method of hercolyn D |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060200C (en) * | 1998-07-16 | 2001-01-03 | 中国科学院广州化学研究所 | Catalytic esterification method of rosin |
-
1999
- 1999-04-28 CN CN99116159A patent/CN1074444C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424146C (en) * | 2002-08-30 | 2008-10-08 | 大日本油墨化学工业株式会社 | Drier for printing ink and printing ink containing the drier |
| CN100387667C (en) * | 2006-02-07 | 2008-05-14 | 福州大学 | Rosin-modified resin of high-boiling alcohol lignin or its derivatives and preparation method thereof |
| CN107573850A (en) * | 2017-09-18 | 2018-01-12 | 广西众昌树脂有限公司 | The preparation method of hercolyn D |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1074444C (en) | 2001-11-07 |
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