CN1073545C - Process for catalytic esterification of maleopimaric acid - Google Patents
Process for catalytic esterification of maleopimaric acid Download PDFInfo
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- CN1073545C CN1073545C CN98113391A CN98113391A CN1073545C CN 1073545 C CN1073545 C CN 1073545C CN 98113391 A CN98113391 A CN 98113391A CN 98113391 A CN98113391 A CN 98113391A CN 1073545 C CN1073545 C CN 1073545C
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- China
- Prior art keywords
- rosin
- maleopimaric acid
- esterification
- present
- acid
- Prior art date
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- Expired - Fee Related
Links
- 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 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 17
- 230000032050 esterification Effects 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims description 13
- 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 abstract description 18
- 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 abstract description 18
- 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 abstract description 18
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- -1 maleopimaric acid ester Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 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 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000011973 solid acid Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 3
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical class CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- 230000009466 transformation Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000000211 1-dodecanols Chemical class 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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 belongs to a method for catalytically esterifying rosin and derivatives thereof. The esterification modification of the rosin and the derivates thereof is the best way to use rosin resources, and the present invention provides a new method for efficiently and catalytically synthesizing maleopimaric acid ester. Stannous oxalate is used as esterification catalysts, and the present invention has the advantages of high rate of catalytic reactions, high yield, no corrosion to devices, good quality of products. The unfavorable factors of poor activity of traditional protonic acid catalysts and solid acid catalysts, multiple side reaction, long reaction time, high energy consumption, environmental pollution, etc. are eliminated, catalytic reaction time is greatly shortened, and production process is simplified. The present invention is favorable for decreasing production cost, and the esterification modification process of maleopimaric acid can be more suitable for the requirements of the production and the development of modern chemical engineering.
Description
The invention belongs to the method for catalytic esterification rosin and derivative thereof.
Rosin is the high yield resource of China, as a kind of natural resin of excellent property, has obtained using widely.Esterification modification is one of most important means of fundamental sum that improve rosin and derivative utility value thereof.Various rosin esters account for more than 60% of Abietyl modified product, are crucial Chemicals.Rosin and maleic anhydride are synthetic suitable-6 by isomery/Diels-Alder addition, 14-dihydro levopimaric acid-6, and 14-bridge-α, β-Succinic anhydried is called for short maleopimaric acid (MPA).MPA and alcohols reaction synthetic maleopimaric acid three esters, on structure, maleopimaric acid is the same with trimellitic anhydride to be tricarboxylic anhydride, has the chemical property of the trimellitic anhydride of being similar to and has higher heat-resisting curve (thermogravimetric curve just begins weightlessness more than 250 ℃).
At present, trimellitic anhydride is widely used in producing the polyester of heat-resisting weather resistance softening agent and polyamidoimide heat-resistant insulation material and used for powder coating, its ternary alcohols is widely used in tamanori, printing ink, coating and plastic plasticizer industry, is a kind of industrial chemicals that supply falls short of demand.Maleopimaric acid ternary ester class has and the akin structure of tri trimellitate ester compound, therefore it is expected to replace trimellitic anhydride to be used as the high temperature plasticizer of macromolecular material, have very strong using value, and because its sky inhibition effect is bigger, performance is better.
The rosin that generally adopts and the esterifying catalyst of derivative thereof have bronsted acid catalyst now, as sulfuric acid, tosic acid and phosphoric acid etc.; Solid acid catalyst such as zinc oxide; Liquid catalyst such as titanate ester etc., the rosin of these catalysts and the esterification reaction tech of derivative thereof need high temperature and condition such as long-time, and ester liquid quality is not fine.At present, synthetic reaction times (" research of the synthetic ester polyol reaction of maleopimaric acid ", the Shang Shibin etc. that generally need 20～30 hours of the catalysis of maleopimaric acid ester class, chemistry of forest product and industry, 1995, Vol.15, No.2, Page1～6), even need pressurized operation.Stannous oxalate catalyst esterification activity is very high, ester liquid quality is good, and consumption is ten thousand of a reactant/can reach catalytic effect preferably.Adopt the stannous oxalate catalyzer, generally need only 1～6 hour, shortened the reaction times greatly, and ester liquid is of light color, good quality.
The objective of the invention is the catalytic esterification field at rosin and derivative thereof, esterifying catalyst efficient by using, high yield in the hope of further simplifying the operation, is saved the energy, raises the efficiency.
Catalytic esterification method provided by the present invention is as follows: add catalyzer in the reaction system of maleopimaric acid and alcohol, stir, heat, temperature control reacted 1～8 hour at 200～260 ℃, after aquifer yield reaches theoretical value, boiled off solvent and can get the maleopimaric acid ester.Transformation efficiency can reach more than 95%.Reacting used catalyzer is stannous oxalate, and consumption is 0.05～2.0% of a maleopimaric acid weight, and optimum amount is 0.1～1.0%; Generally not necessarily adopt solvent dehydration.
Heterogeneous catalytic system preparation method provided by the present invention is as follows: catalyzer is covered in metallic carrier or molecular sieve (or clay, kaolin etc.) surface carries out simultaneously in catalytic esterification.Metallic carrier adopts the stainless steel mesh grid that contains small additions of chromium and nickel; Molecular sieve adopts the 13X molecular sieve.List the stainless steel mesh grid in the reactor (or adding a certain amount of molecular sieve, clay, kaolin etc.), add acid, pure and mild excessive catalyzer (be about reaction-ure mixture 0.2%), stirring, fraction water device water-dividing, the control esterification is carried out (about 200～260 ℃) in certain temperature, reacts 1～8 hour.In this process, 70% the catalyzer of having an appointment has formed the catalyzer coverture and has been fixed on the carrier surface.
Wherein said rosin and derivative thereof comprise rosin, nilox resin, staybelite and maleated rosin.
The invention provides a kind of catalytic esterification novel method, novel process of maleopimaric acid, adopt the stannous oxalate esterifying catalyst, rate of catalysis reaction is fast, yield is high, ester liquid quality is good, to the equipment non-corrosiveness.After adopting carrier to solidify (load) catalysis technique, can simplify even can omit the aftertreatment technology of product greatly.
Embodiment 1:
Get 0.5 mole of maleopimaric acid, 1.5 moles of n-Octanols, 0.1 the gram stannous oxalate is inserted in the three neck round-bottomed flasks that thermometer, agitator, reflux exchanger and water trap are housed, with electric mantle heating, stirring, the controlled temperature perseverance is in 210 ℃, clock, after 6 hours, be warmed up to 260 ℃ of reaction 20min, steam n-Octanol, obtain product.Transformation efficiency is greater than 95%.
Embodiment 2:
Get 0.5 mole of maleopimaric acid, 1.5 moles of lauryl alcohols, add 0.2 gram stannous oxalate, an amount of 13X molecular sieve is inserted in the three neck round-bottomed flasks that thermometer, agitator, reflux exchanger and water trap are housed, with electric mantle heating, stirring, the controlled temperature perseverance clocks in 230 ℃, after 6 hours, steam toluene, obtain product.Transformation efficiency is greater than 99%.
Embodiment 3:
Get 0.5 mole of maleopimaric acid, 1.5 moles of phenylcarbinols, add 0.2 gram stannous oxalate, an amount of kaolin or clay are inserted in the three neck round-bottomed flasks that thermometer, agitator, reflux exchanger and water trap are housed, with electric mantle heating, stirring, the control reaction temperature perseverance clocks in 210 ℃, after 1.5 hours, reaction finishes, and obtains product.Transformation efficiency is greater than 99%.
Embodiment 4:
Get 0.5 mole of maleopimaric acid, 1.5 moles of phenylcarbinols, 0.2 gram stannous oxalate and two volume stainless steel mesh grids, insert in the four neck round-bottomed flasks that dropping funnel, thermometer, agitator, reflux exchanger and water trap are housed, with electric mantle heating, stirring, control reaction temperature is in about 220 ℃, reaction was clocked, after 1.5 hours, theoretical amount has been arrived in water outlet in the water trap, steam n-Octanol, stop heating, leave standstill cooling, inclining reaction product, and transformation efficiency is greater than 98%.Behind the catalyst cupport, reuse 5 times, add 0.01 gram catalyzer at every turn, under constant situation of reaction times, transformation efficiency is kept.
Embodiment 5:
Get 0.5 mole of rosin acid, 0.6 mole of n-Octanol, 0.2 gram stannous oxalate, insert in the four neck round-bottomed flasks that dropping funnel, thermometer, agitator, reflux exchanger and water trap are housed, with electric mantle heating, stirring, control reaction temperature is in about 220 ℃, clock, after 2.5 hours, theoretical amount has been arrived in water outlet in the water trap, be warmed up to 260 ℃ of reaction 10min, steam n-Octanol, stop heating, leave standstill and be cooled to 100 ℃, inclining reaction product, and transformation efficiency is greater than 98%.
Embodiment 6:
Get 0.6 mole of rosin acid, 0.2 mole of glycerine, 0.2 gram stannous oxalate, insert in the four neck round-bottomed flasks that dropping funnel, reflux exchanger, thermometer and agitator are housed, with electric mantle heating, stirring, control reaction temperature is in about 240 ℃, clock, 3.5 after hour, theoretical amount has been arrived in water outlet in the water trap, is warmed up to 260 ℃ of reaction 30min, stop heating, leave standstill and be cooled to 100 ℃, inclining reaction product, and transformation efficiency is greater than 95%.
Embodiment 7:
Get 0.4 mole of rosin acid, 0.1 mole of tetramethylolmethane, 0.2 gram stannous oxalate, insert in the four neck round-bottomed flasks that dropping funnel, reflux exchanger, thermometer and agitator are housed, with electric mantle heating, stirring, control reaction temperature clocks in about 260 ℃, behind the 60min, theoretical amount has been arrived in water outlet in the water trap, stops heating, leaves standstill and is cooled to 180 ℃, inclining reaction product, and transformation efficiency is greater than 98%.
Embodiment 8:
Get 0.5 mole of nilox resin resinous acid, 0.6 mole of isooctyl alcohol, 0.2 gram stannous oxalate, an amount of molecular sieve carrier is inserted in the four neck round-bottomed flasks that dropping funnel, thermometer, agitator, reflux exchanger and water trap are housed, with electric mantle heating, stirring, when treating that temperature rises to 220 ℃, control reaction temperature clocks in about 220 ℃, after 4 hours, theoretical amount has been arrived in water outlet in the water trap, steams isooctyl alcohol, stop heating, leave standstill and be cooled to 100 ℃, inclining reaction product, and transformation efficiency is greater than 98%.
Embodiment 9:
Get 0.5 mole of staybelite resinous acid, 0.6 mole of n-Octanol, 0.2 gram stannous oxalate, stainless (steel) wire is inserted in the four neck round-bottomed flasks that dropping funnel, thermometer, agitator, reflux exchanger and water trap are housed, with electric mantle heating, stirring, when treating that temperature rises to 220 ℃, control reaction temperature clocks in about 220 ℃, after 3 hours, theoretical amount has been arrived in water outlet in the water trap, steams n-Octanol, stop heating, leave standstill and be cooled to 100 ℃, inclining reaction product, and transformation efficiency is greater than 98%.
Embodiment 10:
Get 0.5 mole of staybelite resinous acid, 0.6 mole of n-Octanol, 0.2 gram stannous oxalate and 10 gram 13X molecular sieves, insert in the four neck round-bottomed flasks that dropping funnel, thermometer, agitator, reflux exchanger and water trap are housed, with electric mantle heating, stirring, control reaction temperature is in about 220 ℃, after 3 hours, theoretical amount has been arrived in water outlet in the water trap, steam n-Octanol, stop heating, leave standstill and be cooled to 100 ℃, inclining reaction product, and transformation efficiency is greater than 95%.Behind the catalyst cupport, reuse 5 times, the reaction times is constant, and transformation efficiency is respectively 95%, 90%, 86%, 81% and 77%.
Claims (6)
1. the method for the synthetic maleopimaric acid ester of a catalytic esterification, be in the reaction system of maleopimaric acid and alcohols, to add the stannous oxalate catalyzer, it is characterized in that stannous oxalate is covered in metallic carrier or heterogeneous catalytic system is made on the molecular sieve surface, the catalyzer add-on is 0.05%～2.0% of a maleopimaric acid weight, 200～260 ℃ of temperature of reaction were reacted 1～8 hour.
2. according to the method described in the claim 1, it is characterized in that the catalyst levels scope is 0.1%～1.0% of a maleopimaric acid weight.
3. according to the method described in the claim 1, it is characterized in that described method is suitable for the catalytic esterification of rosin and derivative thereof.
4. according to the method described in the claim 1, it is characterized in that rosin and derivative thereof comprise rosin, nilox resin, staybelite and maleated rosin.
5. according to the method described in the claim 1, it is characterized in that described heterogeneous catalytic system carrier comprises nickeliferous and stainless (steel) wire, 13X molecular sieve and kaolin, clay chromium.
6. according to the method described in the claim 1, it is characterized in that the preparation of catalyst system and esterification carry out simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113391A CN1073545C (en) | 1998-10-27 | 1998-10-27 | Process for catalytic esterification of maleopimaric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113391A CN1073545C (en) | 1998-10-27 | 1998-10-27 | Process for catalytic esterification of maleopimaric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1232020A CN1232020A (en) | 1999-10-20 |
| CN1073545C true CN1073545C (en) | 2001-10-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113391A Expired - Fee Related CN1073545C (en) | 1998-10-27 | 1998-10-27 | Process for catalytic esterification of maleopimaric acid |
Country Status (1)
| Country | Link |
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| CN (1) | CN1073545C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332996C (en) * | 2004-12-22 | 2007-08-22 | 中国科学院化学研究所 | Modified butanediol ester poly succinic acid and synthetic method |
| CN100350007C (en) * | 2005-04-24 | 2007-11-21 | 青岛科技大学 | Process for preparing newtrex |
| CN101638476B (en) * | 2009-09-03 | 2012-01-25 | 中国科学院长春应用化学研究所 | Maleopimaric acidyl bivalent tin catalyst for synthesizing polytrimethylene terephthalate and preparation method thereof |
| CN102311544B (en) * | 2010-07-09 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Rosinyl plasticizer and preparation method thereof |
| CN104942481B (en) * | 2015-07-13 | 2017-04-12 | 中国林业科学研究院林产化学工业研究所 | Preparation method of rosin derivative for electronic welding |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5289638A (en) * | 1976-01-22 | 1977-07-27 | Chisso Corp | Synthesis of phthalic acid esters |
| GB2098211A (en) * | 1981-05-07 | 1982-11-17 | Bp Chem Int Ltd | Production of high-boiling esters by catalytic esterification |
| EP0331280A1 (en) * | 1988-01-29 | 1989-09-06 | Pitman-Moore, Inc. | Method for esterifying hindered carboxylic acids |
| US5571938A (en) * | 1993-12-27 | 1996-11-05 | Jakubowycz; Stan | Esterification process using a catalyst consisting of sand, stannous tin and aluminate |
-
1998
- 1998-10-27 CN CN98113391A patent/CN1073545C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5289638A (en) * | 1976-01-22 | 1977-07-27 | Chisso Corp | Synthesis of phthalic acid esters |
| GB2098211A (en) * | 1981-05-07 | 1982-11-17 | Bp Chem Int Ltd | Production of high-boiling esters by catalytic esterification |
| EP0331280A1 (en) * | 1988-01-29 | 1989-09-06 | Pitman-Moore, Inc. | Method for esterifying hindered carboxylic acids |
| US5571938A (en) * | 1993-12-27 | 1996-11-05 | Jakubowycz; Stan | Esterification process using a catalyst consisting of sand, stannous tin and aluminate |
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| Publication number | Publication date |
|---|---|
| CN1232020A (en) | 1999-10-20 |
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