CN1116370C - Esterification process of rosin acid and its derivative - Google Patents
Esterification process of rosin acid and its derivative Download PDFInfo
- Publication number
- CN1116370C CN1116370C CN 00117530 CN00117530A CN1116370C CN 1116370 C CN1116370 C CN 1116370C CN 00117530 CN00117530 CN 00117530 CN 00117530 A CN00117530 A CN 00117530A CN 1116370 C CN1116370 C CN 1116370C
- Authority
- CN
- China
- Prior art keywords
- alcohol
- catalyst
- esterification process
- reaction system
- rosin acid
- 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 - Fee Related
Links
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 24
- 230000032050 esterification Effects 0.000 title claims abstract description 22
- 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 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 239000002689 soil Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- -1 ester class of rosin acid Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 16
- 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 abstract description 11
- 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 abstract description 11
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 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 18
- 238000010438 heat treatment Methods 0.000 description 13
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 238000007639 printing Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
The present invention relates to an esterification process of rosin acid and a derivative thereof. After the rosin is esterified, the defect of rosin resources can be overcome, and the application area of the present invention is widened. However, because of the reason of the catalyst, the current esterification reaction is not ideal. The present invention provides a carrier type rare-earth catalyst, and the esterification reaction which introduces the catalyst has the advantages of short reaction time, low temperature, uniform and transparent esterification products, shallow color, no need of post processing. The present invention provides a new path for the modernization industrial production.
Description
The present invention relates to the esterification process of a class Gum Rosin and derivative thereof.
Rosin is the first afforestation product resource of China, natural resin as a kind of excellent property, be widely used, but rosin is crisp, easy oxidation discoloration, acid number is higher, has hindered its application to a certain extent, and esterification modification is to widen one of most important means of fundamental sum of rosin application approach, Abietyl modified back performance is greatly improved, various rosin esters account for more than 60% of Abietyl modified product, and its polyvalent alcohol is widely used in coating, printing ink, rubber, industries such as tackiness agent are as tackifier, and the monobasic alcohol ester can be used as rubber and plastic processing additives, and the rosin that generally adopts and the catalyzer of derivative thereof have zinc oxide etc. now, use arts demand high temperature (250～300 ℃) reaction times of these catalyzer to grow (7～11h) (modern chemical industries, 1994,2, p43).
The objective of the invention is to provide a kind of catalyzer of efficient, less energy-consumption, with rosin acid and derivative thereof ester class by synthetic rosin acid of catalytic esterification efficient, less energy-consumption and derivative thereof for the rosin esterification modified industry.
The rosin acid that this is bright and esterification of derivatives reaction thereof are quoted new catalyst and are mainly carried Ln
2O
3/ Al
2O
3Alkene soil catalyst, wherein Ln represents the rare-earth element of atomic number between 57～71, especially Nd, Sm, Gd, La, Eu, Er etc., as highly active abietic resin acid esterification catalyst, adopt carried alkene soil catalyst to compare with conventional catalyst technology, when rosin catalyzed resin acid and esterification of derivatives thereof, reaction time of esterification shortens, reaction temperature obviously reduces, the esterification products homogeneous transparent, lighter color, thus make the esterification modification process of rosin acid and derivative thereof can better be fit to the possibility that develops into of modern production.
Esterification process provided by the present invention comprises following process:
Kaolinite Preparation of Catalyst at first: get a kind of Ln
2O
3(Ln=Nd, Sm, Gd, La, Eu, Er) adds an amount of nitric acid, makes alkene soil nitrate, and other gets the AlCl of metering
3Make the aqueous solution, above-mentioned two kinds of solution are mixed, and use the concentrated ammonia liquor titration, make it to produce precipitation, control its PH=8～10, make Al (OH)
3With Ln (OH)
3Co-precipitation is evenly complete, suction filtration, and oven dry in 800 ℃ of oven dry 1 hour, obtains carried Ln
2O
3/ Al
2O
3Catalyst, this catalyst is joined in the reaction system of rosin acid or derivatives thereof and alcohol, stir, heating, after being warming up to uniform temperature (200～260 ℃), temperature control, reacted 2～6 hours, and after the esterification water yield reaches theoretical value, boiled off the ester that residual solvent and alcohols can get the rosin or derivatives thereof, conversion ratio can reach more than 90%, the consumption of catalyst is 0.05～1.5% of rosin acid or derivatives thereof weight, and the carbon number in the reaction system is 1～18, can adopt solvent dehydration, alcohols in the reaction system is fatty alcohol and aromatic alcohol preferably carbon atom 1-18 alcohols, particularly monohydric alcohol, dihydroxylic alcohols, trihydroxylic alcohol or quaternary alcohols.
Embodiment 1 carried Ln
2O
3/ Al
2O
3Preparation method of catalyst:
Get a kind of Nd2O3 1.0 grams, add an amount of nitric acid (about 5ml) dissolving, it is water-soluble to make alkene soil nitrate, and liquid is got AlCl in addition
310.0 gram is made the aqueous solution, above-mentioned two kinds of solution is mixed, and use the concentrated ammonia liquor titration, makes it to produce co-precipitation, controls its PH=10, makes AL (OH)
3With Nd (OH)
3Co-precipitation is evenly complete, suction filtration Na
2O
3/ Al
2O
3, in 800 ℃ of oven dry 1 hour, obtain carried Nd
2O
3/ Al
2O
3Catalyst.
Embodiment 2:
Get 0.5 mole of rosin acid, 0.6 mole of isooctanol, 2 gram Nd
2O
3/ Al
2O
3Insert in the four neck round-bottomed flasks that dropping funel, thermometer, agitator, reflux condenser and water knockout drum are housed, with electric jacket heating, stirring, when treating that temperature rises to 220 ℃, drip an amount of toluene dehydration in reaction system, the control reaction temperature clocks in about 220 ℃, after 4 hours, theoretical amount has been arrived in water outlet in the water knockout drum; Steam residual toluene and isooctanol; Stopped heating leaves standstill and is cooled to 100 ℃, and inclining product, and conversion ratio is greater than 96%.
Embodiment 3:
Get 0.5 mole of rosin acid, 1..5 restrains Sm
2O
3/ Al
2O
3Insert in the four neck round-bottomed flasks that dropping funel, thermometer, agitator, reflux condenser and water knockout drum are housed, with electric jacket heating, stirring, when treating that temperature rises to 240 ℃, drip the laruyl alcohol of amount of calculation in the reaction system, the control rate of addition remains in about 230 ℃ temperature, clocks, 3.5 after hour, theoretical amount has been arrived in water outlet in the water knockout drum; Steam remaining laruyl alcohol; Stopped heating leaves standstill and is cooled to 100 ℃, and inclining product, and conversion ratio is greater than 94%.
Embodiment 4:
Get 0.5 mole of disproportionated rosin resin acid, 0.3 mole of diethylene glycol (DEG), 0.5 gram Gd
2O
3/ Al
2O
3Insert in the four neck round-bottomed flasks that dropping funel, thermometer, agitator, reflux condenser and water knockout drum are housed, with electric jacket heating, stirring, when treating that temperature rises to 240 ℃, drip an amount of toluene dehydration in reaction system, the control reaction temperature clocks in about 240 ℃, after 4 hours, theoretical amount has been arrived in water outlet in the water knockout drum; Steam residual toluene and diethylene glycol (DEG); Stopped heating leaves standstill and is cooled to 100 ℃, and inclining product, and conversion ratio is greater than 91%.
Embodiment 5: get 0.4 mole of Foral resin acid, 0.1 mole of pentaerythrite, 0.3 gram Eu
2O
3/ Al
2O
3, insert in the four neck round-bottomed flasks that dropping funel, reflux condenser, thermometer and agitator are housed, with electric jacket heating, agitating, the control reaction temperature clocks in about 260 ℃, and behind the 2.5h, theoretical amount has been arrived in water outlet in the water knockout drum; Steam remaining alcohol; Stopped heating leaves standstill and is cooled to 150 ℃, and inclining product, and conversion ratio is greater than 96%.
Embodiment 6:
Get 0.6 mole of rosin acid, 0.2 mole of glycerine, 0.2 gram Er
2O
3/ Al
2O
3, insert in the four neck round-bottomed flasks that dropping funel, reflux condenser, thermometer and agitator are housed, with electric jacket heating, stirring, the control reaction temperature clocks in about 240 ℃, and after 90 minutes, theoretical amount has been arrived in water outlet in the water knockout drum; Steam residual water and glycerine; Stopped heating leaves standstill and is cooled to 150 ℃, and inclining product, and conversion ratio is greater than 98%.
Embodiment 7:
Get 0.5 mole of Foral resin acid, 0.6 mole of phenmethylol, 0.1 gram La
2O
3Insert in the four neck round-bottomed flasks that dropping funel, thermometer, agitator, reflux condenser and water knockout drum are housed, with electric jacket heating, stirring, when treating that temperature rises to 200 ℃, drip an amount of toluene dehydration in reaction system, the control reaction temperature clocks in about 200 ℃, after 90 minutes, theoretical amount has been arrived in water outlet in the water knockout drum; Steam residual toluene and phenmethylol; Stopped heating leaves standstill and is cooled to 100 ℃, and inclining product, and conversion ratio is greater than 97%.
Claims (6)
1, a kind of esterification process of rosin acid or derivatives thereof is characterized in that adding in the reaction system carried Ln
2O
3/ Al
2O
3Alkene soil catalyst, this method comprises following process:
1). Kaolinite Preparation of Catalyst at first: get a kind of Ln
2O
3, add nitric acid and make alkene soil nitrate, with itself and AlCl
3Aqueous solution, with the concentrated ammonia liquor titration it, make it to produce co-precipitation, control PH=8～10, precipitation fully after, suction filtration, oven dry makes Ln
2O
3/ Al
2O
3The type CatalystT.
2). with above-mentioned 1) in the catalyzer that makes join in the reaction system of rosin acid or derivatives thereof and alcohol, catalyst levels is 0.05～1.5% of a rosin acid or derivatives thereof weight, 200～260 ℃ of controlled temperature, reacted 2～6 hours, and obtained the ester class of rosin acid or derivatives thereof.
2, according to the esterification process described in the claim 1, it is characterized in that described carried Ln
2O
3/ Al
2O
3Alkene soil catalyst, wherein Ln represents the rare-earth element of atomic number between 57～71.
3, according to the esterification process described in claim 1 or 2, that it is characterized in that described Ln representative is Nd, Sm, Gd, La, Eu or Er.
4,, it is characterized in that the alcohols in the reaction system comprises Fatty Alcohol(C12-C14 and C12-C18) and aromatic alcohol according to the esterification process described in the claim 1.
5,, it is characterized in that the alcohol in the reaction system is monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, or quaternary alcohols according to the esterification process described in claim 1 or 4.
6,, it is characterized in that alcohol in the reaction system is 1～18 alcohols according to the esterification process described in claim 1 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00117530 CN1116370C (en) | 2000-10-24 | 2000-10-24 | Esterification process of rosin acid and its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00117530 CN1116370C (en) | 2000-10-24 | 2000-10-24 | Esterification process of rosin acid and its derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1350041A CN1350041A (en) | 2002-05-22 |
| CN1116370C true CN1116370C (en) | 2003-07-30 |
Family
ID=4586892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00117530 Expired - Fee Related CN1116370C (en) | 2000-10-24 | 2000-10-24 | Esterification process of rosin acid and its derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1116370C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948415B (en) * | 2010-09-10 | 2013-06-05 | 广西民族大学 | Abietic acid sulfur ether derivative and preparation method thereof |
| CN111826088B (en) * | 2020-08-12 | 2021-12-31 | 广西壮族自治区林业科学研究院 | Production process of high-water-solubility ultra-light-color rosin resin |
-
2000
- 2000-10-24 CN CN 00117530 patent/CN1116370C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1350041A (en) | 2002-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101346409B (en) | Catalyst used for polyester preparation and preparation method of polyester | |
| CN103627326B (en) | A kind of preparation method of rosin ester | |
| CN1492894A (en) | Metal-containing composition and process therewith | |
| CN111087595B (en) | High-activity titanium polyester catalyst and preparation method thereof | |
| CN113881027B (en) | Titanium polyester catalyst and preparation method and application thereof | |
| CN107868238B (en) | Preparation method and application of heavy metal-free polyester polycondensation catalyst | |
| CN106008266B (en) | Green preparation method of hydroximic acid rare earth flotation reagent | |
| CN103011200A (en) | Preparation method of high-concentration cyanamide solution | |
| CN102151583A (en) | Method for preparing vanadium phosphate catalyst used in reaction of acrylic acid synthesized by acetic acid and formaldehyde | |
| CN101077856A (en) | Method for preparing nonane diacid catalyzed by solid acid | |
| CN102603536A (en) | Synthetic method of 3-nitrophthalic acid | |
| CN111170982B (en) | Method for improving selectivity of cyclohexanone oxidation reaction product epsilon-caprolactone | |
| CN1116370C (en) | Esterification process of rosin acid and its derivative | |
| CN111518226A (en) | Preparation method of printing paste for direct printing of reactive dye | |
| US6720448B2 (en) | Method of recovering chemical species by depolymerization of poly (ethylene terephthalate) and related use | |
| EP0894082B1 (en) | Synthesis of solid, powdery rare earth carboxylates by a precipitation method | |
| CN109503402A (en) | A kind of preparation method of green chelating agent | |
| US6670503B2 (en) | Method for recovery of terephthalic acid from a material containing poly(ethylene terephthalates) | |
| CN102631940B (en) | Composite catalyst and application thereof in preparing pale rosin glyceride | |
| CN1074444C (en) | Rosin catalyzed by rare-earth metal oxide and method of esterification of derivatives thereof | |
| CN111484608B (en) | Preparation method capable of producing PBT resin stably for long period | |
| CN114181219A (en) | Application method of alkyl polyoxyethylene ether in copper phthalocyanine synthesis process | |
| CN107502470A (en) | A kind of synthetic fiber spinning hot-rolling cleaning agent and preparation method thereof | |
| CN1060200C (en) | Catalytic esterification method of rosin | |
| CN104448262B (en) | A kind of polymer blend and its manufacturing method and purposes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |