CN1067051C - Method for preparing bridged ring dibasic acid anhydride di-esters - Google Patents
Method for preparing bridged ring dibasic acid anhydride di-esters Download PDFInfo
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- CN1067051C CN1067051C CN98113235A CN98113235A CN1067051C CN 1067051 C CN1067051 C CN 1067051C CN 98113235 A CN98113235 A CN 98113235A CN 98113235 A CN98113235 A CN 98113235A CN 1067051 C CN1067051 C CN 1067051C
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- estolide
- bridged ring
- dibasic acid
- acid anhydride
- dyadic
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Abstract
The present invention relates to a new method for synthesizing dyadic estolide diester by the catalysis and the esterification of an organic stannum compound. A compound of which the structure is similar to that of phthalic diester by an esterification reaction of bridge ring dyadic estolide, and a plasticizing agent used as a high molecular material has strong application value. In the prior art, a catalyst of the esterification reaction of the estolide is mostly protonic acid, and thus, the catalyst has the disadvantages of multiple side reactions of the reaction, inexhaustive reactions, equipment corrosion and environmental pollution. The present invention uses the organic stannum compound as an esterification catalyst, the bridge ring dyadic estolide is reacted with alcohol for 1 to 8 hours at control temperature to obtain dyadic estolide diester containing a bridge ring. The method overcomes the insufficient of the esterification reaction of the bridge ring estolide in the prior art, and has a certain application value.
Description
The present invention relates to the method for the synthetic bridged ring dibasic acid anhydride di-esters compounds of organic tin compound for catalysis esterification.
Turps has rich natural resource in China, directly is utilized as the master with resource for a long time always.Therefore turps being carried out deep processing, to improve its added value be a job that is significant.Turps and homologue thereof all can pass through isomery/Diels-Alder addition synthetic 1-sec.-propyl-4-methyl bicyclic [2,2,2] octene-2,3-dicarboxylic anhydride and 5-sec.-propyl-8-methyl bicyclic [2,2,2] octene-2,3-dicarboxylic anhydride with maleic anhydride; They just are used to do curing agent for epoxy resin as far back as the eighties, make Resins, epoxy can give full play to its distinctive excellent properties.The high yield synthetic method that bibliographical information bridged ring acid anhydrides is all arranged both at home and abroad is for application of the present invention provides reliable bridged ring acid anhydrides source (US 4055576, CAN 1072565, " research and development of natural products " Vol 9, No 1,19 (1997)).
The bridged ring dibasic acid diester that the esterification of bridged ring dibasic acid anhydride obtains has and the akin structure of phthalate compound, and the softening agent that is used as macromolecular material has higher using value.And the anhydride esterifying catalysts of the overwhelming majority mostly is a protonic acid, and side reaction is many, reaction is not thorough and shortcomings such as etching apparatus, contaminate environment and the protonic acid catalytic esterification has.Esterification process advantage provided by the present invention can make simplified control, saves the energy, raise the efficiency, and has reduced the pollution to environment.
The objective of the invention is bridged ring dibasic acid anhydride, by the synthetic novel macromolecular material softening agent of a class of catalytic esterification method efficient, high yield, promptly bridged ring dibasic acid anhydride di-esters is reached the saving energy, the purpose of raising the efficiency.
The method for making that contains bridged ring dibasic acid anhydride di-esters provided by the present invention realizes as follows: will contain and add tin alkyl acids catalyzer in the reaction system of bridged ring dibasic acid anhydride and alcohols, add-on is 0.1～5.0% of a bridged ring dibasic acid anhydride weight, and optimum amount is 0.5～2.0% (bridged ring dibasic acid anhydride weight); Under temperature of reaction, react 1～8 hour after, boil off solvent, obtain bridged ring dibasic acid anhydride di-esters.The carbonatoms of the alcohols in the reaction system is 1～18, particularly 4～12; The carbonatoms of alkyl is 1～18 in the tin alkyl acids catalyzer, particularly 4～12.
Embodiment 1:
Get 1-sec.-propyl-4-methyl bicyclic [2,2,2] octene-2,0.5 mole of 3-dicarboxylic anhydride, 1.0 moles of n-Octanols, 0.5 gram butyl stannonic acid, insert in the four neck round-bottomed flasks that dropping funnel, reflux exchanger, thermometer and agitator are housed, with electric mantle heating, stirring, when treating that temperature rises to 210 ℃, clock, the control reaction temperature perseverance after 2 hours, is warmed up to 260 ℃ in 210 ℃, steam n-Octanol, obtain product.Transformation efficiency is greater than 98%.
Embodiment 2:
Get 5-sec.-propyl-8-methyl bicyclic [2,2,2] octene-2,0.5 mole of 3-dicarboxylic anhydride, 1.0 moles of lauryl alcohols add 0.5 gram phenyl stannic acid, insert in the four neck round-bottomed flasks that dropping funnel, reflux exchanger, thermometer and agitator are housed, with electric mantle heating, stirring, when treating that temperature rises to 210 ℃, drip an amount of toluene in reaction system, the control dripping quantity makes the reflux temperature perseverance in 210 ℃, clocks, after 2 hours, be warmed up to 260 ℃, steam toluene, obtain product.Transformation efficiency is greater than 98%.
Embodiment 3:
Get 1-sec.-propyl-4-methyl bicyclic [2,2,2] octene-2,0.5 mole of 3-dicarboxylic anhydride, 0.2 mole of n-hexyl alcohol, 0.5 gram octyl group stannic acid, insert in the four neck round-bottomed flasks that dropping funnel, reflux exchanger, thermometer and agitator are housed, with electric mantle heating, stirring, when treating that temperature rises to 210 ℃, drip 0.8 mole of n-hexyl alcohol in reaction system, the control rate of addition makes the temperature perseverance in 210 ℃, clocks, after 5 hours, be warmed up to 260 ℃ of reaction 30min, steam n-hexyl alcohol, obtain product.Transformation efficiency is greater than 95%.
Embodiment 4:
The methyne acid anhydrides is 0.5 mole in getting, and 1.1 moles of isooctyl alcohol add 0.3 gram stannoacetic acid, insert in the four neck round-bottomed flasks that dropping funnel, reflux exchanger, thermometer and agitator are housed, with electric mantle heating, stirring, when treating that temperature rises to 190 ℃, clock, after 5 hours, after decompression steams isooctyl alcohol, naturally cool to room temperature, product is with 1～5% NaOH solution washing three times, water layer discarded, oil reservoir wash with water to neutrality again, obtain product after the drying.Product purity is greater than 99%.
Claims (4)
1. the method for a catalytic esterification bridged ring dibasic acid anhydride, comprise bridged ring dibasic acid anhydride and alcohol reaction, it is characterized in that in the reaction system that contains bridged ring dibasic acid anhydride and alcohols, adding the alkyl tin acid compounds and make catalyzer, add-on is 0.1～5.0% of a bridged ring dibasic acid anhydride weight, controlled temperature, reacted 1～8 hour, wherein the carbonatoms of alcohols is 1～18 in the reaction system, and the carbonatoms of alkyl is 1～18 in the alkyl tin acid compounds.
2. according to the method described in the claim 1, the carbonatoms that it is characterized in that alkyl in the described alkyl tin acid compounds is 4～12.
3. according to the method described in the claim 1, the carbonatoms that it is characterized in that alcohols in the reaction system is 4～12.
4. according to the method described in the claim 1, it is characterized in that the catalyzer add-on is 0.5%～2.0% of a bridged ring dibasic acid anhydride weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113235A CN1067051C (en) | 1998-06-05 | 1998-06-05 | Method for preparing bridged ring dibasic acid anhydride di-esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113235A CN1067051C (en) | 1998-06-05 | 1998-06-05 | Method for preparing bridged ring dibasic acid anhydride di-esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1204642A CN1204642A (en) | 1999-01-13 |
| CN1067051C true CN1067051C (en) | 2001-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98113235A Expired - Fee Related CN1067051C (en) | 1998-06-05 | 1998-06-05 | Method for preparing bridged ring dibasic acid anhydride di-esters |
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| CN (1) | CN1067051C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102701982B (en) * | 2012-05-31 | 2016-04-27 | 烟台恒迪克能源科技有限公司 | A kind of method utilizing Terpineol 350 by-product terpinene to synthesize tackifier monomer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3041051B2 (en) * | 1995-10-10 | 2000-05-15 | ファイザー・インコーポレーテッド | NK-1 receptor antagonist for prevention of neurogenic inflammation in gene therapy |
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- 1998-06-05 CN CN98113235A patent/CN1067051C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3041051B2 (en) * | 1995-10-10 | 2000-05-15 | ファイザー・インコーポレーテッド | NK-1 receptor antagonist for prevention of neurogenic inflammation in gene therapy |
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| CN1204642A (en) | 1999-01-13 |
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