CN100480229C - Preparation and application of tetraisopropyl carboxylate - Google Patents
Preparation and application of tetraisopropyl carboxylate Download PDFInfo
- Publication number
- CN100480229C CN100480229C CNB2006101552601A CN200610155260A CN100480229C CN 100480229 C CN100480229 C CN 100480229C CN B2006101552601 A CNB2006101552601 A CN B2006101552601A CN 200610155260 A CN200610155260 A CN 200610155260A CN 100480229 C CN100480229 C CN 100480229C
- Authority
- CN
- China
- Prior art keywords
- tetraisopropyl
- carboxylate
- diisopropyl malonate
- isopropyl
- reaction
- 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
- 150000007942 carboxylates Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- VODRWDBLLGYRJT-UHFFFAOYSA-N propan-2-yl 2-chloroacetate Chemical compound CC(C)OC(=O)CCl VODRWDBLLGYRJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 235000007715 potassium iodide Nutrition 0.000 claims description 9
- 229960004839 potassium iodide Drugs 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- JIWKGERWMRGPQM-UHFFFAOYSA-N propan-2-yl acetate hydrobromide Chemical compound CC(C)OC(C)=O.Br JIWKGERWMRGPQM-UHFFFAOYSA-N 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000008031 plastic plasticizer Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 2
- WWXUGNUFCNYMFK-UHFFFAOYSA-N Acetyl citrate Chemical compound CC(=O)OC(=O)CC(O)(C(O)=O)CC(O)=O WWXUGNUFCNYMFK-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 26
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 11
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 7
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004902 Softening Agent Substances 0.000 description 4
- -1 citric acid ester Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ULWQQRIRULDCNI-UHFFFAOYSA-N C(C)(C)OC(C)=O.[Br] Chemical compound C(C)(C)OC(C)=O.[Br] ULWQQRIRULDCNI-UHFFFAOYSA-N 0.000 description 2
- 235000016936 Dendrocalamus strictus Nutrition 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- YWOITFUKFOYODT-UHFFFAOYSA-N methanol;sodium Chemical compound [Na].OC YWOITFUKFOYODT-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- JXHDZGPVOXKUSI-UHFFFAOYSA-N propane-1,2,2,3-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)(C(O)=O)CC(O)=O JXHDZGPVOXKUSI-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is preparation process and application of tetraisopropyl carboxylate. Diisopropyl malonate and isopropyl chloroacetate as the initial material are one-step reacted under the action of strong alkali and catalyst to synthesize tetraisopropyl carboxylate. After reaction, the reaction product is filtered, water washed to eliminate inorganic salt and decompression distilled to obtain the product. Tetraisopropyl carboxylate is colorless or yellowish transparent liquid, and has structure similar to that of triisopropyl acetyl citrate, plasticizing efficiency and cold resistance similar to that of DOP and compatibility higher than that of DOP. The present invention is used as plasticizer.
Description
Technical field
The present invention relates to the preparation method and the application thereof of tetraisopropyl carboxylate.
Background technology
Along with the raising of countries in the world environmental consciousness, plastics such as medicine and food product pack, daily necessities, toy have proposed higher purity and hygienic requirements to primary plasticizer dioctyl phthalate (DOP) DOP etc.There is the potential carcinogenic danger in DOP, has begun in the world to take appropriate measures, and the use range of restriction DOP: U.S. environment protection general bureau has stopped the industrial production of 6 kinds of phthalic ester plasticizers according to the result of study of National Cancer Institute; Switzerland's government decided bans use of DOP in toy for children; Germany bans use of DOP in all plastics relevant with human body, wholesome food; In Japan, DOP only limits to use in the industrial plastic goods as additives for plastics.China is Asia area plasticizer production amount and the maximum country of consumption, but at present the primary plasticizer produced of domestic enterprise on many performances particularly aspect such as health, hypotoxicity all be difficult to satisfy environmental protection requirement.Therefore, accelerate the research and development dynamics of non-toxic plasticizer product, particularly accelerate exploitation, popularization and the propaganda of the high new plasticizer of hygienic requirements become the task of top priority of state internal plasticizer enterprise.
The citrate series products is present universally acknowledged nontoxic " green " environmentally-friendly plastic softening agent, be widely used in food and medical instrumentation package, makeup, daily necessities, toy, military supplies etc., have that consistency is good, plasticizing efficiency is high, nontoxic, easily by advantage such as biological degradation and volatility be little, photostabilization and having excellent water-resistance, and shock resistance is arranged in resin, do not grow advantages such as mould.The prior synthesizing method of citric acid ester plasticizer is to use citric acid and corresponding alcohol to prepare in the presence of as the sulfuric acid of catalyzer, its raw material citric acid is main at present to adopt microbe fermentation method to prepare, this method technological process is longer, particularly produce a large amount of organic pollutants and solid waste, these pollutents are contaminate environment not only, and quantity discharged is big.Therefore environmental problem always is the principal element of restriction citric acid industry development for a long time, and then has also influenced the extensive promotion and application of citric acid ester plasticizer.If can or have the compound of similar structures by the direct synthesizing citric acid ester of chemical process, will greatly promote the marketing and the widespread use of citric acid ester plasticizer.
Summary of the invention
The object of the present invention is to provide a kind of structure compound close: propane-1 with acetyl tributyl citrate three isopropyl esters, 2,2,3-tetracarboxylic acid isopropyl ester (Tetraisopropyl Propane-1,2,2,3-Tetracarboxylate, synthetic method TIPTC) and as the application of new plasticizer.
Purpose of the present invention is achieved through the following technical solutions:
With Diisopropyl malonate and chlorine (or bromine) isopropyl acetate is starting raw material, under highly basic and catalyst action, through the synthetic TIPTC of single step reaction, after reaction finishes after filtration or washing remove inorganic salt, promptly get product through underpressure distillation again.The gained material is colourless or slightly yellowy transparent liquid, and TIPTC is structurally similar to acetyl tributyl citrate three isopropyl esters.Plasticising performance contrast experiment by TIPTC and DOP can find, novel compound TIPTC plasticizing efficiency, cold tolerance etc. be in same level with DOP, consistency is slightly better than DOP, these The performance test results show that TIPTC meets the every requirement as softening agent fully, are a kind of softening agent of new texture.
The plasticising performance compares:
The available following general formula of reaction of the present invention is represented:
The chemical structure of acetyl tributyl citrate three isopropyl esters is as follows:
The synthetic TIPTC of the present invention comprises following concrete steps:
A, hydrocarbyl reaction
The Diisopropyl malonate that in the three-necked bottle that induction stirring, thermometer, reflux condensing tube (on add drying tube) are housed, adds 0.10mol, amount of methanol sodium (methyl alcohol) or sodium ethylate (ethanol) solution, after temperature reaction 10-60 minute, add little amount of catalyst potassiumiodide or iodine, begin to drip an amount of isopropyl chloracetate or isopropyl acetate bromide then, the dropping time is 10-80 minute, dropwises 3-24 hour stopped reaction of back back flow reaction.
The separation of B, inorganic salt and the purifying of product
Separation and purifying can be undertaken by two kinds of methods, a kind of method is that direct filtration goes out inorganic salt, air distillation goes out methyl alcohol or ethanol and low-boiling point material, the cut of boiling spread is collected in underpressure distillation then, promptly get final product TIPTC: another kind of method is the inorganic salt that are dissolved in water and separate out in the mixture behind hydrocarbyl reaction, separate oil reservoir, dry back underpressure distillation is collected the boiling spread product and is got the finished product.
The preparation method of tetraisopropyl carboxylate specifically may further comprise the steps:
1) in the three-necked bottle that induction stirring, thermometer, reflux condensing tube are housed, stir down Diisopropyl malonate is joined in the methanol solution of sodium methylate or alcohol sodium alcohol solution that mass percent concentration is 15.0-32.0%, the mol ratio of Diisopropyl malonate and sodium methylate or sodium ethylate is 1:2.0-3.0, is warming up to 50-100 ℃ of reaction 10-60 minute;
2) add catalyzer potassiumiodide or iodine, the mass ratio of potassiumiodide or iodine and Diisopropyl malonate is 1:50-400;
3) drip isopropyl chloracetate or isopropyl acetate bromide, the mol ratio of isopropyl chloracetate or isopropyl acetate bromide and Diisopropyl malonate is 2.00-2.05:1, and the dropping time is 10-80 minute, and 50-100 ℃ was reacted 3-24 hour, and reduced to room temperature then;
4) separation and purifying can be undertaken by two kinds of methods, and a kind of method is that direct filtration goes out inorganic salt, and air distillation goes out methyl alcohol or ethanol and low-boiling point material, and the cut of boiling spread is collected in underpressure distillation then, promptly gets final product TIPTC; Another kind method is the inorganic salt that are dissolved in water and separate out in the mixture behind hydrocarbyl reaction, separates oil reservoir, and dry back underpressure distillation is collected the boiling spread product and got final product TIPTC.
With synthetic the comparing of background technology citric acid three ester class softening agent, advantage of the present invention is:
(1) reaction conditions gentleness, the reaction times is shorter;
(2) do not use citric acid to be starting raw material, be not subjected to the restriction of citric acid market supply;
(3) do not have obvious waste discharge, having only NaCl or NaBr is by product;
(4) last handling process is simple;
(5) do not use the material of containing benezene, and traditional citrate synthetic often uses toluene etc. to be the band aqua.
Embodiment
Embodiment 1:
1) under the stirring Diisopropyl malonate being joined mass percent concentration is in 19.0% alcohol sodium alcohol solution, and the mol ratio of Diisopropyl malonate and sodium ethylate is 1:2.0, is warming up to 85 ℃ of reactions 30 minutes;
2) add the catalyzer potassiumiodide, the mass ratio of potassiumiodide and Diisopropyl malonate is 1:100;
3) dripping bromine isopropyl acetate, the mol ratio of isopropyl acetate bromide and Diisopropyl malonate are 2.01:1, and the dropping time is 20 minutes, and 85 ℃ were reacted 3 hours, and reduced to room temperature;
4) inorganic salt that are dissolved in water and separate out are isolated underpressure distillation behind the oil reservoir, collect the boiling spread product, reclaim unreacted raw material and etoh solvent simultaneously.In the Diisopropyl malonate productive rate is 90%.
Embodiment 2:
1) stirring is that 19.0% methanol solution of sodium methylate joins in the Diisopropyl malonate with mass percent concentration down, and the mol ratio of Diisopropyl malonate and sodium methylate is 1:2.1, is warming up to 75 ℃ of reactions 20 minutes;
2) add catalyst simple substance iodine, the mass ratio of iodine and Diisopropyl malonate is 1:200;
3) drip isopropyl chloracetate, the mol ratio of isopropyl chloracetate and Diisopropyl malonate is 2.05:1, and the dropping time is 30 minutes, and 75 ℃ were reacted 8 hours, and reduced to room temperature;
4) filter the inorganic salt of separating out, the boiling spread product is collected in underpressure distillation, reclaims unreacted raw material and solvent methanol simultaneously.In the Diisopropyl malonate productive rate is 86%.
Embodiment 3:
1) stirring is that 18.0% alcohol sodium alcohol solution joins in the Diisopropyl malonate with mass percent concentration down, and the mol ratio of Diisopropyl malonate and sodium ethylate is 1:2.0, is warming up to 80 ℃ of reactions 20 minutes;
2) add the catalyzer sodium iodide, the mass ratio of sodium iodide and Diisopropyl malonate is 1:110;
3) dripping bromine isopropyl acetate, the mol ratio of isopropyl acetate bromide and Diisopropyl malonate are 2.02:1, and the dropping time is 20 minutes, and 80 ℃ were reacted 4 hours, and reduced to room temperature;
4) inorganic salt that are dissolved in water and separate out are isolated underpressure distillation behind the oil reservoir, collect the boiling spread product, reclaim unreacted raw material and etoh solvent simultaneously.In the Diisopropyl malonate productive rate is 87%.
Embodiment 4:
1) under the stirring Diisopropyl malonate being joined mass percent concentration is in 20.0% methanol solution of sodium methylate, and the mol ratio of Diisopropyl malonate and sodium methylate is 1:2.2, is warming up to 75 ℃ of reactions 10 minutes;
2) add the catalyst simple substance potassiumiodide, the mass ratio of potassiumiodide and Diisopropyl malonate is 1:100;
3) drip isopropyl chloracetate, the mol ratio of isopropyl chloracetate and Diisopropyl malonate is 2.04:1, and the dropping time is 15 minutes, and 75 ℃ were reacted 6 hours, and reduced to room temperature;
4) filter the inorganic salt of separating out, the boiling spread product is collected in underpressure distillation, reclaims unreacted raw material and solvent methanol simultaneously.In the Diisopropyl malonate productive rate is 83%.
The example that TIPTC uses as plastic plasticizer is as follows:
With polyvinyl chloride (PVC) powder, TIPTC, one package stabilizer and colorant can be made into the leatheroid surface layer after mixing by mass ratio 100:52:3:20, coat foaming layer again and promptly make leatheroid.
Claims (2)
1, a kind of preparation method of tetraisopropyl carboxylate is characterized in that may further comprise the steps:
1) in the three-necked bottle that induction stirring, thermometer, reflux condensing tube are housed, stir down Diisopropyl malonate is joined in the methanol solution of sodium methylate or alcohol sodium alcohol solution that mass percent concentration is 15.0-32.0%, the mol ratio of Diisopropyl malonate and sodium methylate or sodium ethylate is 1:2.0-3.0, is warming up to 50-100 ℃ of reaction 10-60 minute;
2) add catalyzer potassiumiodide or iodine, the mass ratio of potassiumiodide or iodine and Diisopropyl malonate is 1:50-400;
3) drip isopropyl chloracetate or isopropyl acetate bromide, the mol ratio of isopropyl chloracetate or isopropyl acetate bromide and Diisopropyl malonate is 2.00-2.05:1, and the dropping time is 10-80 minute, and 50-100 ℃ was reacted 3-24 hour, and reduced to room temperature then;
4) separation and purifying are undertaken by two kinds of methods, and the one, direct filtration goes out inorganic salt, and air distillation goes out methyl alcohol or ethanol and low-boiling point material, and the cut of boiling spread is collected in underpressure distillation then, promptly gets the final product tetraisopropyl carboxylate; Or the inorganic salt that are dissolved in water and separate out in the mixture behind hydrocarbyl reaction, separating oil reservoir, dry back underpressure distillation is collected the boiling spread product and is got the final product tetraisopropyl carboxylate; Its structural formula is
2, the application of tetraisopropyl carboxylate according to claim 1, it is characterized in that: tetraisopropyl carboxylate uses as plastic plasticizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101552601A CN100480229C (en) | 2006-12-13 | 2006-12-13 | Preparation and application of tetraisopropyl carboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101552601A CN100480229C (en) | 2006-12-13 | 2006-12-13 | Preparation and application of tetraisopropyl carboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1974531A CN1974531A (en) | 2007-06-06 |
| CN100480229C true CN100480229C (en) | 2009-04-22 |
Family
ID=38124923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101552601A Expired - Fee Related CN100480229C (en) | 2006-12-13 | 2006-12-13 | Preparation and application of tetraisopropyl carboxylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100480229C (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275975A (en) * | 1997-05-12 | 2000-12-06 | 莱利工业公司 | Processes for producing citrate esters |
| US6310234B1 (en) * | 1997-08-29 | 2001-10-30 | Rwe-Dea Aktiengesellschaft Fuer Mineraloel Und Chemie | Esters of aromatic polycarboxylic acids with 2-alkylalkan-1-ols |
| EP1449823A1 (en) * | 2001-10-10 | 2004-08-25 | Kyowa Yuka Co., Ltd. | Dibasic acid diester |
| DE102004034202A1 (en) * | 2004-07-14 | 2005-11-10 | Sasol Germany Gmbh | Ester mixture obtained by esterification of dicarboxylic acid in presence of tri-/tetra-carboxylic acid with mono-hydroxy alcohol, useful as e.g. lubricant, hydraulic fluid, comprises alcohol, carbonic acids and dicarbonic acid |
-
2006
- 2006-12-13 CN CNB2006101552601A patent/CN100480229C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275975A (en) * | 1997-05-12 | 2000-12-06 | 莱利工业公司 | Processes for producing citrate esters |
| US6310234B1 (en) * | 1997-08-29 | 2001-10-30 | Rwe-Dea Aktiengesellschaft Fuer Mineraloel Und Chemie | Esters of aromatic polycarboxylic acids with 2-alkylalkan-1-ols |
| EP1449823A1 (en) * | 2001-10-10 | 2004-08-25 | Kyowa Yuka Co., Ltd. | Dibasic acid diester |
| DE102004034202A1 (en) * | 2004-07-14 | 2005-11-10 | Sasol Germany Gmbh | Ester mixture obtained by esterification of dicarboxylic acid in presence of tri-/tetra-carboxylic acid with mono-hydroxy alcohol, useful as e.g. lubricant, hydraulic fluid, comprises alcohol, carbonic acids and dicarbonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1974531A (en) | 2007-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102079704B (en) | Preparation method of triethyl citrate | |
| CN102153482B (en) | Method for refining injection-level ambroxol hydrochloride, product and injection thereof | |
| CN102503845A (en) | Preparation method of DL-lysine aspirin salt and application thereof | |
| WO2015039409A1 (en) | Synthesis process for diacetyl epoxy glyceryl oleate | |
| CN102993146B (en) | Method for continuously synthesizing coumarin by using microchannel reactor | |
| CN102766050A (en) | Method for synthesizing dimethyl fumarate | |
| CN103012150A (en) | Method for preparing plasticizer 1, 2, 4-benzenetricarboxylicacid tris(2-propyl heptyl) ester | |
| CN101973951A (en) | Chiral D-oxazoline and application thereof | |
| CN1974532B (en) | Prepn and application of diisopropyl diethyl carboxylate | |
| CN100480229C (en) | Preparation and application of tetraisopropyl carboxylate | |
| CN101012167A (en) | Carboxylate and its preparing method and application | |
| CN100480230C (en) | Preparation and application of diethyl diisopropyl carboxylate | |
| CN100537512C (en) | Preparation and application of isopropyl diethyl carboxylate | |
| CN100453521C (en) | Prepn and application of ethyl diisopropyl carboxylate | |
| CN1974530B (en) | Prepn and application of triisopropyl carboxylate | |
| CN103012313A (en) | Synthetic method of aminothiazoly loximate | |
| CN104774161A (en) | Peptide and protein pegylation agent synthesis method | |
| CN103030560A (en) | Catalyzing and decoloring integrated method for synthesizing environment-friendly plasticizer triethylhexyl (2-propylheptyl) citrate | |
| CN108047032B (en) | Method for the synthesis of glutaric acid from alpha-ketoglutaric acid | |
| CN102010327A (en) | Splitting method of (+/-)-2-(3-benzoyl)-phenylpropionic acid | |
| CN101003480B (en) | Ethane 1,1,2 - ethyl ester tricarboxylic acid, preparation method, and application as plasticizer | |
| CN104292222A (en) | Novel synthetic method of tebipenem pivoxil side chain | |
| CN102010345A (en) | Method for preparing D-phenylalanine through dynamic kinetic resolution | |
| CN100473682C (en) | Application of propane 1, 2, 2, 3 - ethyl ester tetracarboxylic acid as plasticizer, and preparation method thereof | |
| CN106542961B (en) | A kind of synthetic method of racecadotril intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090422 Termination date: 20111213 |