CN1611563A - Liquid antioxidant and its preparing method - Google Patents
Liquid antioxidant and its preparing method Download PDFInfo
- Publication number
- CN1611563A CN1611563A CN 200310103033 CN200310103033A CN1611563A CN 1611563 A CN1611563 A CN 1611563A CN 200310103033 CN200310103033 CN 200310103033 CN 200310103033 A CN200310103033 A CN 200310103033A CN 1611563 A CN1611563 A CN 1611563A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- side chain
- described preparation
- catalyzer
- alcohol
- 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.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229940006116 lithium hydroxide Drugs 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 229940093932 potassium hydroxide Drugs 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract description 8
- 230000005494 condensation Effects 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 235000006708 antioxidants Nutrition 0.000 abstract 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000003112 inhibitor Substances 0.000 description 12
- 238000004821 distillation Methods 0.000 description 9
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 229940017219 methyl propionate Drugs 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- -1 Phenolic ester Chemical class 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Then invention relates to a kind of liquid anti-oxidant with the structure of type (1). Among (1), R1 and R2 is C1-C8 alkyl, m is 0, 1, 2 or 3, and A is C12-C32 alkyl with a branched chain; the branched chain is in beta of fundamental chain, and C number difference of branched chain and fundamental chain is 4. In the invention, make oxyphenyl carboxylic ester react with Guerber alcohol of 10-32 C number in the condition of catalyst, in 80-240deg.C, in order to get the liquid anti-oxidant. The liquid anti-oxidant is liquid in ordinary temperature, and it has low condensation point, low volatilization, and high oxygen resistance, so that it is convenient for practical application and allotment.
Description
Technical field
The present invention relates to oxidation inhibitor and preparation thereof.
Background technology
Along with petrochemical complex, rubber and plastics, the development of macromolecular material and food-processing industry, more and more higher to the requirement of oxidation inhibitor.All there are problem of oxidation in the manufacturing of multiple organic materials, storage, processing and use, and adding oxidation inhibitor is to make it to have necessary resistance of oxidation in order to prevent material aging, and therefore the character requirement to antioxidant is: (1) solvability; (2) volatility; (3) stability; (4) nondiscoloration and pollution; (5) physicals.
Phenolic ester type oxidation inhibitor is that a class is used oxidation inhibitor widely, and its production technique is simple, but molecular weight is lower, and mostly is solid.Is known by β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and straight-chain higher alcohol by the method that transesterification reaction prepares the phenolic ester type antioxidant.For example JP 06135897 discloses a kind of preparation method, be that the employing lithium hydroxide is a catalyzer, at 160 ℃, be decompressed under 20～30mmg condition, by β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and n-stearyl alcohol were carried out transesterification reaction one hour, be cooled to 100 ℃, remove by filter lithium hydroxide, cooling back recrystallization, obtain solid β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester.
Liquid antioxidant is easy to use, and material compatibility is good.The general molecular weight of existing liquid phenolic ester type oxidation inhibitor is lower, the volatility height; If be reaction raw materials according to the method described above with the straight-chain higher alcohol, then can only obtain solid phenolic ester oxidation inhibitor.
Summary of the invention
The liquid antioxidant that the purpose of this invention is to provide a kind of high carbon number, low volatilization, low condensation point.
Another object of the present invention provides the preparation method of above-mentioned oxidation inhibitor.
Liquid antioxidant provided by the invention has following structure:
Wherein R1 and R2 are C
1-C
8Alkyl, preferred C
1-C
4Alkyl, R1 and R2 can be identical, also can be different; M is 0,1,2 or 3, preferred 2; A is that carbon number is C
12-C
32The alkyl that has a side chain, side chain is in the β position of main chain, and the carbon number of side chain and main chain differs 4.
The preparation method of liquid antioxidant provided by the invention comprises:
With hydroxyphenyl carboxylic acid esters and the carbon number of structural formula (II) expression is 12-32, and the Guerbet alcohol of preferred 16-28 reacts in 80-240 ℃ under the effect of catalyzer, separates also collection product.
Wherein R1 and R2 are C independent of each other
1-C
8Alkyl, preferred C
1-C
4Alkyl, m are 0,1,2 or 3, preferred 2.
Said Guerbet alcohol (Guerbet alcohol) is the alkyl alcohol that has side chain, and side chain is in the β position of main chain, and the carbon number of side chain and main chain differs 4.Guerbet alcohol is generally formed by the low-carbon alcohol dimerization.The carbon number of the Guerbet alcohol that the present invention selects for use is 12-32, is preferably 16-28, can be the alcohol mixture of different carbon numbers, and the low-carbon alcohol that is used for the polymerization Guerbet alcohol also can be an alcohol mixture.
Said catalyzer is the catalyzer that is used for transesterification reaction, can be salt, oxide compound or the oxyhydroxide of basic metal well known in the art, alkaline-earth metal or subgroup metallic element, and organometallic compound etc., for example potassium hydroxide, lithium hydroxide, magnesium acetate, zinc sulfate, tetraisopropoxy titanium, alkyl-tin oxide etc.
Specifically, the preparation method's of Guerbet alcohol provided by the invention temperature of reaction is 80 ℃-240 ℃, is preferably 120 ℃-180 ℃, and reaction pressure can normal pressure or decompression, and pressure range can be between the 0.01-0.1MPa.In reaction process, to remove the methyl alcohol of generation.React after 1-12 hour, unreacted raw material is removed in distillation or underpressure distillation, and product is filtered, and separating catalyst and other solid impurities promptly get the target product liquid antioxidant.
Guerbet alcohol (Guerbet alcohol) can be by stoichiometric reaction with hydroxyphenyl carboxylic acid esters, and any all can be suitably excessive when feeding intake, and excessive raw material can be removed by underpressure distillation.
Catalyst consumption is the 0.1-5% of hydroxyphenyl carboxylic acid esters weight, preferred 0.25-2%.
Liquid antioxidant provided by the invention carries out transesterification reaction with Guerbet alcohol and hydroxyphenyl carboxylic acid esters and obtains, and normal temperature is liquid down, low condensation point, and low volatilization, antioxygen is strong, is convenient to practical application and allotment.
Because the target product that the inventive method makes is a liquid, has very low condensation point, therefore when product postprocessing, can be cooled to very low temperature, get final product solid catalyst and other solid impurities with filtering method, and need not to use specific technology to destroy catalyzer, or, simplified postprocessing working procedures with underpressure distillation or method of extraction separating catalyst, save cost, improved production efficiency.
Description of drawings
Fig. 1 is the chemical shift theoretical value of β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid 20 carbon Ge Shi alcohol esters.
Fig. 2 is the nmr spectrum of implementation column 2 products.
Fig. 3 is the nmr spectrum of implementation column 5 products.
Embodiment
Present embodiment is the preparation of Guerbet alcohol.
The 500g decyl alcohol is inserted in the reaction flask, mechanical stirring, thermometer, water trap, prolong are housed in the reaction flask.Add 15 gram KOH and 1.0 gram nickel, fully stir down, be heated to 250 ℃ as early as possible, refluxed four hours, remove the water that generates in the dereaction, cold filtration, distillation obtains C20 Ge Shi alcohol.
The pure and mild C16 Ge Shi of the C24 Ge Shi alcohol that uses the same method and can make, just reaction raw materials changes the pure and mild octanol of 12 carbon into.
Embodiment 2
0.5 mole C20 Ge Shi alcohol 149g of embodiment 1 system and β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 146g of 0.5 mole are inserted in the 500ml four-hole reaction flask, mechanical stirring, thermometer, water trap, prolong are housed in the reaction flask.Add 0.15 moles of hydrogen Lithium Oxide 98min 1.25g, heating is decompressed to 0.085MPa, and temperature is 160 ℃, reacted 4.2 hours, and be warming up to 240 ℃, the raw material that there is not reaction is removed in underpressure distillation, is cooled to room temperature, filter, obtain light yellow liquid product 259.32g, yield 92.95%.Product is done application of gas chromatorgraphy/mass, determines not have β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate content 5.5% of reaction, product 93.0%, molecular weight of product is 558, and the mass spectrum molecular ion peak is 558.7, relative abundance 37%, (instrument is a U.S. TRACEMS mass spectrograph, four-electrode spectrum, EI source).Product is done nucleus magnetic resonance and is determined chemical structure behind column chromatographic isolation and purification, and the chemical shift theoretical value is seen Fig. 1, and the nuclear-magnetism spectrum is seen Fig. 2.
With 0.5 mole C20 Ge Shi alcohol 149g of embodiment 1 system and 0.7 mole β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 146g inserts in the reaction flask identical with embodiment 2, add tetraisopropoxy titanium 1.25g, heating, be decompressed to 0.087MPa, temperature is 160 ℃, reacts 3.6 hours.Be cooled to 110 ℃, add 10ml water, stir, slowly temperature rising reflux to 140 ℃ removes and anhydrates, and is warming up to 240 ℃, and the raw material that there is not reaction is removed in underpressure distillation, is cooled to room temperature, filters, and obtains light yellow liquid product 251.6g, yield 90.18%.Gas-chromatography is determined product content 95.0%.
0.65 mole C16 Ge Shi alcohol 156g that embodiment 1 is made and 0.5 mole β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 146g inserts in the reaction flask identical with embodiment 2, adds potassium hydroxide 1.5g, heating, be decompressed to 0.093MPa, temperature is 155 ℃, reacts 5.7 hours, and the raw material that there is not reaction is removed in the intensification underpressure distillation, be cooled to room temperature, filter, obtain yellow liquid product 228.99g, yield 91.2%.Product is done mass spectrum, and molecular weight of product is 502, and the mass spectrum molecular ion peak is 503, relative abundance 27%.
Embodiment 5
With 0.5 mole C24 Ge Shi alcohol 177g of embodiment 1 system and 0.5 mole β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 146g inserts in the reaction flask identical with embodiment 2, adds 0.15 moles of hydrogen Lithium Oxide 98min 1.5g, heating, be decompressed to 0.094MPa, temperature is 178 ℃, reacts 4.7 hours, and the raw material that there is not reaction is removed in the intensification underpressure distillation, be cooled to room temperature, filter, obtain light yellow liquid product 284.81g, yield 92.77%.The nuclear-magnetism spectrum is seen Fig. 3.
Embodiment 6
Present embodiment is the antioxidant property test.
Add 1% oxidation inhibitor respectively in the base oil of a kind of 150SN, estimate antioxidant property with PDSC, used instrument is the DSC2910 type analysis instrument of U.S. TA company, test conditions is sample size 2.000mg, oxygen pressure 5atm, 190 ℃, it is as follows to measure oxidation induction period:
| Sample | Base oil | T501 | Starting ester | Embodiment 2 | | Embodiment 5 |
| Inductive phase (min) | ＜2.8 | ?6.14 | ?10.84 | ?14.70 | ?12.69 | ?11.61 |
Annotate: T501 is the oxidation inhibitor 2,6 ditertiary butyl p cresol of using always, and starting ester is β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate.
Find out that from experimental data oxidation inhibitor of the present invention has better antioxidant property.
Embodiment 7
Present embodiment is the condensation point test.
Measure the condensation point of above-mentioned sample, determination data is as follows:
| Sample | Starting | Contrast ester | 1 | Embodiment 2 | | Embodiment 5 |
| The normal temperature outward appearance | Yellow solid | White solid | Light yellow liquid | Yellow liquid | Light yellow liquid | |
| Condensation point, ℃ | ------ | 49～54 | -38 | -37 | -35 |
Annotate: contrast ester 1 is commodity oxidation inhibitor β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid first stearyl alcohol ester, and its stearyl alcohol is a straight chain alcohol, and above data are its product description data.
Find out that from above data product of the present invention has lower condensation point.
Embodiment 8
Present embodiment is the volatile performance test.
Measure above-mentioned sample thermal weight loss, estimate volatile performance, used instrument is the TGA2950 type thermogravimetric analyzer of U.S. TA company, and air flow quantity 60ml/min, heat-up rate are 5 ℃/min.Determination data is as follows:
| Sample | ????T501 | Starting ester | Contrast ester 2 | Embodiment 2 | Embodiment 5 | |||||
| Temperature ℃ | 81.9 | ?166.6 | ?125.6 | ?216.7 | ?148.2 | ?258.9 | ?227.5 | ?365.0 | ?216.7 | ??364.0 |
| Quality % | 98.95 | ?0.29 | ?98.72 | ?0.29 | ?98.34 | ?1.27 | ?90.85 | ?9.97 | ?92.17 | ??11.55 |
Annotate: contrast ester 2 is the 2-Ethylhexyl Alcohol ester of β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid.
Claims (10)
1. liquid antioxidant has following structure:
Wherein R1 and R2 are C
1-C
8Alkyl, m are 0,1,2 or 3, and A is C
12-C
32The alkyl that has a side chain, side chain is in the β position of main chain, the carbon number of side chain and main chain differs 4.
2. according to the described liquid antioxidant of claim 1, it is characterized in that R1 and R2 are C
1-C
4Alkyl, m are 2, and A is C
16-C
28The alkyl that has a side chain, side chain is in the β position of main chain, the carbon number of side chain and main chain differs 4.
3. the preparation method of the described liquid antioxidant of claim 1, comprise: the Guerbet alcohol that the hydroxyphenyl carboxylic acid esters and the carbon number of structural formula (II) expression is 12-32 reacts in 80-240 ℃ under the effect of catalyzer, separate and the collection product, wherein R1 and R2 are C
1-C
8Alkyl, m are 0,1,2 or 3.
4. according to the described preparation method of claim 3, it is characterized in that the carbon number of Guerbet alcohol is 16-28.
5. according to the described preparation method of claim 3, it is characterized in that R1 and R2 are C
1-C
4Alkyl, m are 2.
6. according to the described preparation method of claim 3, it is characterized in that said catalyzer is the catalyzer that is used for transesterification reaction.
7. according to claim 3 or 6 described preparation methods, it is characterized in that said catalyzer is salt, oxide compound or the oxyhydroxide of basic metal, alkaline-earth metal, organometallic compound and subgroup metallic element.
8. according to claim 3 or 6 described preparation methods, it is characterized in that said catalyzer is potassium hydroxide, lithium hydroxide, magnesium acetate, zinc sulfate, tetraisopropoxy titanium or alkyl-tin oxide.
9. according to the described preparation method of claim 3, it is characterized in that catalyst consumption is the 0.1-5% of hydroxyphenyl carboxylic acid esters weight.
10. according to the described preparation method of claim 3, it is characterized in that temperature of reaction is 120 ℃-180 ℃, reaction pressure is 0.01-0.1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310103033 CN1247737C (en) | 2003-10-31 | 2003-10-31 | Liquid antioxidant and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310103033 CN1247737C (en) | 2003-10-31 | 2003-10-31 | Liquid antioxidant and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1611563A true CN1611563A (en) | 2005-05-04 |
| CN1247737C CN1247737C (en) | 2006-03-29 |
Family
ID=34756505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310103033 Expired - Lifetime CN1247737C (en) | 2003-10-31 | 2003-10-31 | Liquid antioxidant and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1247737C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476995A (en) * | 2010-11-25 | 2012-05-30 | 中国石油化工股份有限公司 | Preparation method of liquid hindered phenol carboxylic ester antioxidant |
| WO2020078369A1 (en) | 2018-10-16 | 2020-04-23 | 中国石油化工股份有限公司 | Phenolic derivative, preparation method therefor and use thereof |
| CN111057025A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Phenol derivative and preparation method and application thereof |
| CN114426464A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Phenol derivative and preparation method and application thereof |
-
2003
- 2003-10-31 CN CN 200310103033 patent/CN1247737C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476995A (en) * | 2010-11-25 | 2012-05-30 | 中国石油化工股份有限公司 | Preparation method of liquid hindered phenol carboxylic ester antioxidant |
| CN102476995B (en) * | 2010-11-25 | 2014-05-28 | 中国石油化工股份有限公司 | Preparation method of liquid hindered phenol carboxylic ester antioxidant |
| WO2020078369A1 (en) | 2018-10-16 | 2020-04-23 | 中国石油化工股份有限公司 | Phenolic derivative, preparation method therefor and use thereof |
| CN111057025A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Phenol derivative and preparation method and application thereof |
| US11787757B2 (en) | 2018-10-16 | 2023-10-17 | China Petroleum & Chemical Corporation | Phenol derivative, and preparation process and use thereof |
| CN114426464A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Phenol derivative and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1247737C (en) | 2006-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Brown et al. | Improved procedure for the asymmetric reduction of prochiral ketones by B-3-pinanyl-9-borabicyclo [3.3. 1] nonane | |
| CN1247737C (en) | Liquid antioxidant and its preparing method | |
| CN1034818C (en) | Extractant for separating rare-earth metal | |
| CN101056841A (en) | Method for preparing asymmetric linear carbonate | |
| CN1314654C (en) | Method for synthesizing phenyloxalate from dicthyl oxalate and phenol | |
| CN1039993C (en) | Method for preparing hydroxyphenyl-carboxylic ester | |
| CN117142926A (en) | Preparation method of 3,5-di-tert-butylphenol | |
| CN1162589A (en) | Process for manufacture of alpha-beta-unsaturated organic carboxylic acids | |
| US20080295393A1 (en) | Method for the production of biodiesel from vegetable oils and fats, using heterogeneous catalysts | |
| CN1042128C (en) | Process for preparation of alcohols | |
| CN102603491A (en) | Clean production method for preparing bisphenol antioxidant | |
| CN1305990A (en) | Method for improving mercapto phenol | |
| CN1308279C (en) | Purification method of 6,10,14-trimethyl-5E, 9E, 13-pentadecatricene-2-ketone | |
| CN1733691A (en) | Industrial synthesis method of 3,5-di tertiary butyl-4-hydroxyl phenyl methyl propionate | |
| CN1107848A (en) | Preparation of imidazopyridir derivative | |
| CN1269827C (en) | Method for synthesizing iridium (III) triacetylacetonate | |
| CN1247504C (en) | Process for preparing beta-halogen-alpha-phenyl ethyl alcohol compounds | |
| CN111302919A (en) | Method for synthesizing high-content dihydrojasmone spice | |
| CN101066913A (en) | Process of synthesizing bis (trihydroxy methyl propane) | |
| CN1872831A (en) | Method for preparing key intermediate of medication for anti AIDS | |
| CN113831591B (en) | Novel efficient hindered phenol antioxidant and preparation method thereof | |
| CN1733781A (en) | Methyl rhenium trioxide synthesis method | |
| CN1958573A (en) | Method for preparing compound of 1, 2 (dodecyl) 4 hydroxide methylene - 3, 5 pyrazole | |
| CN1157358C (en) | Process for synthetizing 2,2-demethyl-3-(1-propenyl) cyclopropane carboxylic ester | |
| CN1024657C (en) | Process for preparing salicylal from salicylcohol by catalytic oxidation of non-noble metal complex |
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 | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060329 |