CN106631782A - Preparation method of pentaerythritol tetrabasic acid ester - Google Patents
Preparation method of pentaerythritol tetrabasic acid ester Download PDFInfo
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- CN106631782A CN106631782A CN201610901836.8A CN201610901836A CN106631782A CN 106631782 A CN106631782 A CN 106631782A CN 201610901836 A CN201610901836 A CN 201610901836A CN 106631782 A CN106631782 A CN 106631782A
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- Prior art keywords
- pentaerythrite
- preparation
- acid esters
- crude product
- quaternary
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- 239000002253 acid Substances 0.000 title claims abstract description 117
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 150000002148 esters Chemical class 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000012043 crude product Substances 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 31
- 238000005886 esterification reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002250 absorbent Substances 0.000 claims description 25
- 230000002745 absorbent Effects 0.000 claims description 25
- 230000032050 esterification Effects 0.000 claims description 18
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 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 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000011973 solid acid Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 238000012360 testing method Methods 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002199 base oil Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- 150000004665 fatty acids Chemical class 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 8
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 229940005605 valeric acid Drugs 0.000 description 4
- BWMXRNGZUDOSJR-UHFFFAOYSA-N 3,3,5-trimethylhexanoic acid Chemical compound CC(C)CC(C)(C)CC(O)=O BWMXRNGZUDOSJR-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010725 compressor oil Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 neopentyl polyol ester Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of pentaerythritol tetrabasic acid ester. The method includes the steps of: a) mixing pentaerythritol, fatty acid and a catalyst to perform an esterification reaction to prepare a pentaerythritol tetrabasic acid ester crude product; and b) mixing the pentaerythritol tetrabasic acid ester crude product with a solid adsorbent to purify the crude product to obtain the pentaerythritol tetrabasic acid ester. Compared with the prior art, the preparation method can effectively remove impurities in the reaction system, so that the pentaerythritol tetrabasic acid ester has excellent high temperature performance. A test result proves that the content of impurity elements in the pentaerythritol tetrabasic acid ester prepared through the method is lower than 1 ppm. In addition, the pentaerythritol tetrabasic acid ester has better oxidizing performance, wherein the initial oxidization temperature thereof is increased by more than 10 DEG C in the same base oil.
Description
Technical field
The present invention relates to chemical technology field, is to be related to a kind of preparation side of pentaerythrite quaternary acid esters more specifically
Method.
Background technology
Pentaerythrite quaternary acid esters is a kind of important neopentyl polyol ester, because its ester group quantity is more and quaternary carbon atom
β positions on without hydrogen atom, hexatomic ring resonant structure can be formed with hydroxyl oxygen, and there is good oxidation stability, thermally-stabilised
Property, low temperature flow and viscosity-temperature characteristics energy, are widely used in aeroengine oil, automotive lubricant, air compressor oil and fire-resistant hydraulic pressure
The fields such as oil.
The synthetic method of pentaerythrite quaternary acid esters mainly has esterification process, chloride method and ester-interchange method, wherein, esterification process tool
There are process is simple, low cost and other advantages, become the most frequently used synthetic method in this area.At present, esterification process disclosed in prior art
In order that esterification is completely, using excessive aliphatic acid, while also remaining catalyst and a small amount of in esterification reaction product
Half ester, be ensure properties of product require, need by filter, diminishing wash and distill as major way refinement treatment process removal
Impurity in system.
But, above-mentioned esterification process not only complex process, and through subtracting water-washing process after, may be because of the residual meeting of a small amount of alkali
Cause pentaerythrite quaternary acid esters to decompose at high temperature, affect the high-temperature behavior of product, bring new to the combination property of product
Negative effect.
The content of the invention
In view of this, it is an object of the invention to provide a kind of preparation method of pentaerythrite quaternary acid esters, it is possible to increase
The high-temperature behavior of pentaerythrite quaternary acid esters.
The invention provides a kind of preparation method of pentaerythrite quaternary acid esters, comprises the following steps：
A) pentaerythrite, aliphatic acid and catalyst are mixed, carries out esterification, obtain pentaerythrite quaternary acid esters thick
Product；
B) pentaerythrite quaternary acid esters crude product is mixed with solid absorbent, carries out refinement treatment, obtain pentaerythrite four
First acid esters.
Preferably, aliphatic acid described in step a) is the one kind or many in 1～10 saturated fatty acid selected from carbon number
Kind.
Preferably, catalyst described in step a) includes stannous oxalate, stannous oxide and solid acid SO4 2-/Al2O3In one
Plant or various.
Preferably, the amount ratio of pentaerythrite, aliphatic acid and catalyst described in step a) is 1mol：(4～5) mol：(2
～6) g.
Preferably, the temperature of esterification described in step a) be 120 DEG C～220 DEG C, vacuum be -0.095MPa～-
0.03MPa, the reaction time is 3h～8h.
Preferably, the acid number of pentaerythrite quaternary acid esters crude product described in step b) is 0.1mgKOH/g～0.5mgKOH/
g。
Preferably, solid absorbent described in step b) includes atlapulgite, aluminum oxide, hydrotalcite, 4A molecular sieves, 5A point
One or more in son sieve, inorganic silica gel and activated carbon supported type solid base.
Preferably, pentaerythrite quaternary acid esters crude product described in step b) and the mass ratio of solid absorbent are 1：(0.5%
～5%).
Preferably, the process of refinement treatment is specially described in step b)：
To filter after the mixture stirring of pentaerythrite quaternary acid esters crude product and solid absorbent, obtain pentaerythrite quaternary
Acid esters.
Preferably, the temperature of the stirring is 70 DEG C～140 DEG C, and the time is 0.5h～3h.
The invention provides the invention provides a kind of preparation method of pentaerythrite quaternary acid esters, comprises the following steps：
A) pentaerythrite, aliphatic acid and catalyst are mixed, carries out esterification, obtain pentaerythrite quaternary acid esters crude product；B) by season
Penta tetrol quaternary acid esters crude product mixes with solid absorbent, carries out refinement treatment, obtains pentaerythrite quaternary acid esters.With existing skill
Art is compared, and the preparation method that the present invention is provided can effectively remove the impurity in reaction system, so that the season penta for preparing
Tetrol quaternary acid esters has good high-temperature behavior.Test result indicate that, the Ji Wusi that the preparation method that the present invention is provided is obtained
Alcohol quaternary acid esters impurity content is less than 1ppm, and oxidation susceptibility is more preferably, and same base oil, initial oxidation temperature improves 10
More than DEG C.
In addition, the preparation method process is simple that the present invention is provided, produces admittedly without waste liquid with useless, and product appearance obtains bright
It is aobvious to improve.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only a part of embodiment of the invention, rather than the embodiment of whole.Based on the embodiment in the present invention,
The every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, belongs to this
The scope of bright protection.
The invention provides a kind of preparation method of pentaerythrite quaternary acid esters, comprises the following steps：
A) pentaerythrite, aliphatic acid and catalyst are mixed, carries out esterification, obtain pentaerythrite quaternary acid esters thick
Product；
B) pentaerythrite quaternary acid esters crude product is mixed with solid absorbent, carries out refinement treatment, obtain pentaerythrite four
First acid esters.
The present invention first mixes pentaerythrite, aliphatic acid with catalyst.In the present invention, the aliphatic acid is preferably selected from
Carbon number is one or more in 1～10 saturated fatty acid, and more preferably carbon number is 4～10 saturated fatty acid
In one or more, yet more preferably one or more in butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid and capric acid.The present invention
The source of the aliphatic acid is not particularly limited, using commercial goods well known to those skilled in the art.
In the present invention, the catalyst preferably includes stannous oxalate, stannous oxide and solid acid SO4 2-/Al2O3In one
Plant or various, more preferably stannous oxalate and/or stannous oxide.The present invention is not particularly limited to the source of the catalyst,
Using commercial goods well known to those skilled in the art.
The present invention mixes pentaerythrite, aliphatic acid with catalyst, the consumption of the pentaerythrite, aliphatic acid and catalyst
Than being preferably 1mol：(4～5) mol：(2～6) g, more preferably 1mol：(4.2～4.8) mol：(3～5.5) g.
After completing the mixed process, the present invention carries out mixed pentaerythrite, aliphatic acid and catalyst to be esterified instead
Should, obtain pentaerythrite quaternary acid esters crude product.The present invention is not particularly limited to the device of the esterification, it is preferred to use this
Reflux known to art personnel.In the present invention, the temperature of the esterification is preferably 120 DEG C～220
DEG C, more preferably 180 DEG C～210 DEG C；The vacuum of the esterification is preferably -0.095MPa～-0.03MPa, more preferably
For -0.07MPa～-0.05MPa；The reaction time of the esterification is preferably 3h～8h, more preferably 5h～6h.
The present invention carries out under the above-described reaction conditions esterification, and reaction depth is higher, can promote the complete of esterification
Entirely, the pentaerythrite quaternary acid esters crude product for obtaining has relatively low acid number.In the present invention, the pentaerythrite quaternary acid esters crude product
Acid number be preferably 0.1mgKOH/g～0.5mgKOH/g.
It is of the invention by pentaerythrite quaternary acid esters crude product and solid absorption after obtaining the pentaerythrite quaternary acid esters crude product
Agent mixes.In the present invention, the solid absorbent preferably includes atlapulgite, aluminum oxide, hydrotalcite, 4A molecular sieves, 5A point
One or more in son sieve, inorganic silica gel and activated carbon supported type solid base, more preferably atlapulgite, aluminum oxide, neatly
One or more in stone, 4A molecular sieves and 5A molecular sieves.In the present invention, the solid absorbent can effectively remove season penta
A small amount of impurity in tetrol quaternary acid esters crude product, while acid number can further be reduced.The present invention is to the solid absorbent
Source is not particularly limited, using commercial goods well known to those skilled in the art.
In the present invention, the pentaerythrite quaternary acid esters crude product and the mass ratio of solid absorbent are preferably 1：
(0.5%～5%), more preferably 1：(2%～3%).
It is of the invention by mixed season penta after completing the mixing of the pentaerythrite quaternary acid esters crude product and solid absorbent
Tetrol quaternary acid esters crude product carries out refinement treatment with solid absorbent, obtains pentaerythrite quaternary acid esters.In the present invention, it is described
The process of refinement treatment is preferably specially：
To filter after the mixture stirring of pentaerythrite quaternary acid esters crude product and solid absorbent, obtain pentaerythrite quaternary
Acid esters.In the present invention, the mixture of pentaerythrite quaternary acid esters crude product and solid absorbent is stirred.The present invention is to institute
The mode for stating stirring is not particularly limited, equal by the way of mechanical agitation well known to those skilled in the art or artificial stirring
Can, it is therefore an objective to be that mixture is fully contacted, realize solid absorbent to the impurity maximum journey in pentaerythrite quaternary acid esters crude product
The absorption of degree.In the present invention, the temperature of the stirring is preferably 70 DEG C～140 DEG C, more preferably 100 DEG C～120 DEG C；It is described
The time of stirring is preferably 0.5h～3h, more preferably 1h～2h.
After completing the whipping process, the present invention is filtered said mixture, obtains pentaerythrite quaternary acid esters.
In the present invention, the purpose of the filtration is to be separated pentaerythrite quaternary acid esters with solid absorbent.The present invention preferably will
Solid absorbent after separation carries out high-temperature roasting.In the present invention, the temperature of the high-temperature roasting is preferably 300 DEG C～550
DEG C, more preferably 400 DEG C～500 DEG C.By carrying out high-temperature roasting to the solid absorbent, solid absorbent can be realized
Recycle, so as to avoid preparation process in give up solid generation.
The invention provides the invention provides a kind of preparation method of pentaerythrite quaternary acid esters, comprises the following steps：
A) pentaerythrite, aliphatic acid and catalyst are mixed, carries out esterification, obtain pentaerythrite quaternary acid esters crude product；B) by season
Penta tetrol quaternary acid esters crude product mixes with solid absorbent, carries out refinement treatment, obtains pentaerythrite quaternary acid esters.With existing skill
Art is compared, and the preparation method that the present invention is provided can effectively remove the impurity in reaction system, so that the season penta for preparing
Tetrol quaternary acid esters has good high-temperature behavior.Test result indicate that, the Ji Wusi that the preparation method that the present invention is provided is obtained
Alcohol quaternary acid esters impurity content is less than 1ppm, and oxidation susceptibility is more preferably, and same base oil, initial oxidation temperature improves 10
More than DEG C.
In addition, the preparation method process is simple that the present invention is provided, produces admittedly without waste liquid with useless, and product appearance obtains bright
It is aobvious to improve.
In order to further illustrate the present invention, it is described in detail below by following examples.
Embodiment 1
(1) by pentaerythrite 136g, positive valeric acid 48.96g, positive enanthic acid 17.28g, 3,3,5- tri-methyl hexanoic acid 663.6g and
Stannous oxide 5.1g mixes, under 200 DEG C, -0.05MPa vacuums, back flow reaction 5h, then through vacuum depickling, obtain 660g
Pentaerythrite quaternary acid esters crude product, adopts the acid number of GB/T7304 test pentaerythrite quaternary acid esters crude products for 0.5mgKOH/g.
(2) above-mentioned pentaerythrite quaternary acid esters crude product is mixed with 16.5g atlapulgites, 1h is stirred at 100 DEG C, filtered
Atlapulgite, obtains pentaerythrite quaternary acid esters, and the acid number for testing pentaerythrite quaternary acid esters is less than 0.1mgKOH/g.
The pentaerythrite quaternary acid esters for obtaining is carried out into the accelerated oxidation test of oil product, test result indicate that, embodiment 1
The impurity content of the pentaerythrite quaternary acid esters for arriving is less than 1ppm, and oxidation susceptibility is more preferably, same base oil, initial oxidation
Temperature improves more than 10 DEG C；80 DEG C, acid number increases no more than 0.5mgKOH/g within 7 days.
Meanwhile, tested to embodiment 1 using the oil viscosity of GJB563 corrosion and oxidation stability experiment and GB/T 264
The pentaerythrite quaternary acid esters for obtaining is tested, and is as a result shown, the pentaerythrite quaternary acid esters that the embodiment of the present invention 1 is provided
The equal index request of correlated performance；The colourity of the pentaerythrite quaternary acid esters provided using GB/T6540 testing example 1 is not more than
2, product appearance be improved significantly.
Embodiment 2
(1) by pentaerythrite 136g, positive valeric acid 48.96g, caprylic acid 19.5g, 3,3,5- tri-methyl hexanoic acid 663.6g and oxygen
Change the mixing of stannous 5.1g, under 210 DEG C, -0.06MPa vacuums, back flow reaction 6h, then vacuum depickling is carried out, obtain 662g seasons
Penta tetrol quaternary acid esters crude product, the acid number for testing pentaerythrite quaternary acid esters crude product is 0.5mgKOH/g.
(2) above-mentioned pentaerythrite quaternary acid esters crude product is mixed with the 5A molecular sieves of 6.62g, the aluminum oxide of 6.62g,
2h is stirred under 110 DEG C of vacuum condition, solid absorbent is filtered, pentaerythrite quaternary acid esters is obtained, pentaerythrite quaternary is tested
The acid number of acid esters is less than 0.1mgKOH/g.
The pentaerythrite quaternary acid esters for obtaining is carried out into the accelerated oxidation test of oil product, test result indicate that, embodiment 2
The impurity content of the pentaerythrite quaternary acid esters for arriving is less than 1ppm, and oxidation susceptibility is more preferably, and initial oxidation temperature is 227
℃；80 DEG C, acid number increases no more than 0.5mgKOH/g within 7 days.
Embodiment 3
(1) pentaerythrite 136g, positive valeric acid 61.2g, 3,3,5- tri-methyl hexanoic acid 663.6g and stannous oxide 5.1g are mixed
Close, under 180 DEG C, -0.07MPa vacuums, back flow reaction 6.5h, depickling under vacuum condition obtains 652g pentaerythrite quaternarys
Acid esters crude product, the acid number for testing pentaerythrite quaternary acid esters crude product is 0.5mgKOH/g.
(2) above-mentioned pentaerythrite quaternary acid esters crude product is mixed with 19.56g hydrotalcites, 1.5h, mistake is stirred at 120 DEG C
Drainage talcum, obtains pentaerythrite quaternary acid esters, and the acid number for testing pentaerythrite quaternary acid esters is less than 0.1mgKOH/g.
The pentaerythrite quaternary acid esters for obtaining is carried out into the accelerated oxidation test of oil product, test result indicate that, embodiment 3
The impurity content of the pentaerythrite quaternary acid esters for arriving is less than 1ppm, and oxidation susceptibility is more preferably, and initial oxidation temperature is 232
℃；80 DEG C, acid number increases no more than 0.5mgKOH/g within 7 days.
The described above of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.It is right
Various modifications of these embodiments will be apparent for those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
Will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with principles disclosed herein and features of novelty
Most wide scope.
Claims (10)
1. a kind of preparation method of pentaerythrite quaternary acid esters, comprises the following steps：
A) pentaerythrite, aliphatic acid and catalyst are mixed, carries out esterification, obtain pentaerythrite quaternary acid esters crude product；
B) pentaerythrite quaternary acid esters crude product is mixed with solid absorbent, carries out refinement treatment, obtain pentaerythrite tetra-atomic acid
Ester.
2. preparation method according to claim 1, it is characterised in that aliphatic acid is selected from carbon number described in step a)
One or more in 1～10 saturated fatty acid.
3. preparation method according to claim 1, it is characterised in that catalyst described in step a) include stannous oxalate,
Stannous oxide and solid acid SO4 2-/Al2O3In one or more.
4. preparation method according to claim 1, it is characterised in that pentaerythrite, aliphatic acid described in step a) with urge
The amount ratio of agent is 1mol：(4～5) mol：(2～6) g.
5. preparation method according to claim 1, it is characterised in that the temperature of esterification described in step a) is 120
DEG C～220 DEG C, vacuum is -0.095MPa～-0.03MPa, and the reaction time is 3h～8h.
6. preparation method according to claim 1, it is characterised in that pentaerythrite quaternary acid esters crude product described in step b)
Acid number be 0.1mgKOH/g～0.5mgKOH/g.
7. preparation method according to claim 1, it is characterised in that solid absorbent described in step b) includes that activity is white
One kind or many in soil, aluminum oxide, hydrotalcite, 4A molecular sieves, 5A molecular sieves, inorganic silica gel and activated carbon supported type solid base
Kind.
8. preparation method according to claim 1, it is characterised in that pentaerythrite quaternary acid esters crude product described in step b)
It is 1 with the mass ratio of solid absorbent：(0.5%～5%).
9. preparation method according to claim 1, it is characterised in that the process of refinement treatment is concrete described in step b)
For：
To filter after the mixture stirring of pentaerythrite quaternary acid esters crude product and solid absorbent, obtain pentaerythrite tetra-atomic acid
Ester.
10. preparation method according to claim 9, it is characterised in that the temperature of the stirring is 70 DEG C～140 DEG C, when
Between be 0.5h～3h.
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| CN111848397A (en) * | 2019-04-26 | 2020-10-30 | 南京纽邦生物科技有限公司 | Preparation method of pentaerythritol tetraisostearate |
| CN111848403A (en) * | 2019-04-26 | 2020-10-30 | 南京纽邦生物科技有限公司 | Preparation method of pentaerythritol tetraisostearate |
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