CN101475467A - Novel process for synthesizing polyatomic alcohol ester by lipase catalysis - Google Patents
Novel process for synthesizing polyatomic alcohol ester by lipase catalysis Download PDFInfo
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- CN101475467A CN101475467A CNA2009100581901A CN200910058190A CN101475467A CN 101475467 A CN101475467 A CN 101475467A CN A2009100581901 A CNA2009100581901 A CN A2009100581901A CN 200910058190 A CN200910058190 A CN 200910058190A CN 101475467 A CN101475467 A CN 101475467A
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- -1 alcohol ester Chemical class 0.000 title claims abstract description 59
- 108090001060 Lipase Proteins 0.000 title claims abstract description 30
- 239000004367 Lipase Substances 0.000 title claims abstract description 30
- 102000004882 Lipase Human genes 0.000 title claims abstract description 30
- 235000019421 lipase Nutrition 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 23
- 239000000194 fatty acid Substances 0.000 claims abstract description 23
- 229930195729 fatty acid Natural products 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 108090000790 Enzymes Proteins 0.000 claims abstract description 12
- 102000004190 Enzymes Human genes 0.000 claims abstract description 12
- 108010084311 Novozyme 435 Proteins 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims description 20
- 238000005809 transesterification reaction Methods 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 13
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 241001661345 Moesziomyces antarcticus Species 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- 238000000199 molecular distillation Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 241001465754 Metazoa Species 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 150000004665 fatty acids Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 108010048733 Lipozyme Proteins 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 108010093096 Immobilized Enzymes Proteins 0.000 abstract description 2
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 2
- 235000019737 Animal fat Nutrition 0.000 abstract 2
- 235000019871 vegetable fat Nutrition 0.000 abstract 2
- 230000002411 adverse Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 5
- 150000002632 lipids Chemical class 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 239000000314 lubricant Substances 0.000 description 2
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- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- 241000222175 Diutina rugosa Species 0.000 description 1
- 241000235403 Rhizomucor miehei Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
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Abstract
The invention belongs to the technical field of biochemical industry, and relates to a novel process for synthesizing polyol ester by catalysis of lipase. The process is to catalyze an ester exchange reaction of fatty acid low alkanol ester and neopentyl polyol by immobilized lipase in the presence of an organic solvent to synthesize the polyol ester. Tertiary butyl alcohol is added into a reaction system to improve the solubility of substrate, so that the whole reaction system is in homogeneous (except immobilized enzyme), adverse effects of water on enzyme in catalytic activity and stability can also be completely eliminated, the reaction activity and stability of the immobilized lipase Novozym 435 and the immobilized lipase Lipozyme TL IM can be improved so as to remarkably improve the yield of the polyol ester. The fatty acid low alkanol ester adopted by the method can be selected from an alcoholysis product of natural animal and vegetable fat with methanol or ethanol, wherein the natural animal and vegetable fat has rich sources with low cost, and is a renewable resource. The renewable resource with wide sources as a raw material to synthesize the polyol ester has large market potential.
Description
Technical field
The present invention relates to a kind of novel process of synthesizing polyatomic alcohol ester by lipase catalysis, belong to technical field of biochemical industry.
Technical background
Modern lubricating oil is added various additives and is formed mostly by the base oil more than 86%.Base oil is undoubtedly lubricating oil influences environment or ecological deciding factor.Along with the mouth benefit raising of development of modern industry and environmental requirement, synthetic ester has obtained using more and more widely because of its unique high temperature performance, viscosity temperature characteristic, lubricity, biodegradable performance as the base oil of high performance lubricant.Not only be used for military field at present abroad, and be widely used in industrial circles such as automobile, petrochemical complex, metallurgy, machinery to remedy the defective of mineral oil on some performance.The development of synthetic ester is that the development with aircraft industry is closely connected together.Reached the suitable stage of maturity in the research aspect the ester class oil abroad.For adapting to the develop rapidly of aero engine technology, need improve constantly the thermal load ability to bear of lubricating oil in esters.Around this key problem in technology, carried out fruitful fundamental research.Synthesize the dibasic acid esters that high temperature performance is better than Dormant oils in early days, synthesize the better neopentyl polyol ester of high-temperature behavior afterwards again.
Enter 21 century, the demand of synthetic ester continues steady-state growth, and the demand of synthetic ester is more and more big, and annual growth reaches about 15%.Mainly contain the factor of following several respects: at first be that high-tech development is harsher to the requirement of lubricant.The volume-diminished of mechanical means, the increase of loading, precision improve, prolong work-ing life, require the lubricating oil consumption few, simultaneously energy high-and low-temperature resistance, heavy loading, long lifetime.And synthetic ester oil grease has characteristics such as consumption is few, steam output is little, additional amount is few, and the life-span is long, can satisfy the needs of harsh lubricating condition.The multi-stage combustion engine of for example big viscosity span oil 5W/50,10W/50 have only the full synthetic oil requirement that just can touch the mark.Secondly, because shortage of resources, universal demand is energy-conservation.And synthetic ester can utilize the animal-plant oil preparation, has enlarged raw material sources, has good friction reducing effect simultaneously, can play the purpose of saving the petroleum resources and the energy.At last, higher along with requirement on environmental protection, more comprehensively.Mineral oil can not biological degradation, and synthetic ester has good biodegradability, can satisfy the environmental requirement of new millennium.
Neopentyl polyol ester is by the product of amyl-based polyol (comprising dimethyltrimethylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, dipentaerythritol etc.) with straight chain or branched fatty acid response.Polyol ester not only satisfies renewable and requirement this two aspect of biodegradable, also has the unrivaled high-performance of petroleum base lubricating oil: the 1. liquid range of broad, higher viscosity index, good viscosity performance and low-temperature performance; 2. heat-resistant quality is good, and heat decomposition temperature is more than 310 ℃; 3. the ester group group that contains greater activity in the molecular structure is easy to be adsorbed on the metallic surface and forms firm oil-bound film, has friction, lubrication characteristic preferably.
At present the synthetic method of polyol ester has two kinds of esterification process and ester-interchange methods, and esterification process typically uses an acidic catalyst, and as sulfuric acid, hydrochloric acid, phosphoric acid, right-toluene sulfonic acide, Phenylsulfonic acid etc., catalysis lipid acid and polyvalent alcohol carry out esterification; Ester-interchange method adopts fatty acid methyl ester at alkali (CH usually
3OCa etc.) the following and polyol reaction of effect.Though chemical catalyst can make reaction obtain comparatively ideal esterification yield, but use the method for chemical catalyst to have following deficiency: 1) reaction is often with such as side reactions such as oxidation, carbonization, polymerization, rearrangements, poor selectivity, by product is many in the reaction, the product postprocessing complex process, the esterified prod purification difficult, the production cost height, and influence quality product; 2) complex process needs alkali neutralization, washing, and quantity of wastewater effluent is big, and environmental pollution is serious; 3) catalyzer is harmful, and equipment corrosion is serious, and catalyzer is difficult to reclaim; 4) temperature of reaction height, unsaturated fatty acids is at high temperature apt to deteriorate, and product color is darker, the energy consumption height.
Adopt biological enzyme agent synthesis for polyol ester to have advantages such as reaction conditions gentleness, no coupling product, product are easy to collect,, non-pollutant discharge simple to equipment requirements.But the subject matter that exists is cost height, the life-span weak point of enzyme at present, and transformation time is long etc.
The relevant at present report of biological enzyme agent synthesis for polyol ester that adopts is few, at [Linko, Y.-Y., T.Tervakangas, M.
And P.Linko, Product ion of trimethylolpropaneesters of Rapeseed Oil Fatly Acids by Immobilized Lipase, BiotechnologyTechniques, Vol 11, No 11, November 1997, pp.889-892.] report in the document: TriMethylolPropane(TMP) (2-ethyl-2-methylol-1, ammediol) adopts fixed lipase catalyzed transesterification reaction with the rapeseed oil fatty acid methyl esters, under the situation of not adding organic solvent and water, with immobilized lipase Lipozyme IM 20 (deriving from Rhizomucor miehei) at 58 ℃, 5.3kPa, react the highest transformation efficiency of 66h polyol ester approximately to 90%.Lipase Candida rugosa is fixed on the ion exchange resin 561 at 47 ℃, 5.3kPa, the transformation efficiency of reaction 78h polyol ester is approximately 70%, and Zui Jia amount of water is 13% of a substrate quality in this case.And with immobilized lipase Novozyme 435 (deriving from Candia antarctic) under same reaction conditions, at 66h, only have the trace polyol ester.Its major cause is that Novozyme 435 is the immobilized lipases that are used for nonaqueous system, this kind of enzyme is for many than Lipozyme IM 20 sensitivities of the water-content in the reaction mixture, when water content is too much in the reaction system, can change the active structure of enzyme, reduce the catalytic activity of enzyme, influence speed of reaction.
Chinese invention patent (application number: 200710120622.8) disclose with immobilized inferior sieve and separated fat yeast fat enzyme, under the situation of organic solvent or inorganic solvent, catalytic polyol and unary fatty acid esterification, the highest transformation efficiency to 95.779% of reaction 24h.
Because the source difference of lipase, also there is very big-difference in its catalysis characteristics.Compare with ester-interchange method is raw materials used from the esterification process of synthesis for polyol ester, adopt fatty acid methyl ester or fatty-acid ethyl ester to have following advantage than lipid acid: the thermo-sensitivity of (1) fatty acid methyl ester or fatty-acid ethyl ester is better than lipid acid; (2) fatty acid methyl ester or fatty-acid ethyl ester are lower than lipid acid to the requirement of equipment.Therefore, develop the novel process of new lipase-catalyzed ester-interchange method synthesis for polyol ester, the yield that reduces the use cost raising polyol ester of lipase is the key that realizes industrialization Production by Enzymes polyol ester.
Summary of the invention
The objective of the invention is to propose a kind of novel process of synthesizing polyatomic alcohol ester by lipase catalysis.This technology is to utilize immobilized lipase under the condition that organic solvent exists, the transesterification reaction synthesis for polyol ester of catalysis fatty acid ester and amyl-based polyol.It is characterized in that:
(1) transesterification reaction: with mol ratio is that 2: 1～4: 1 fatty acid ester and amyl-based polyol joins in the Rotary Evaporators, and adding immobilized lipase and organic solvent, wherein the dosage of immobilized lipase is 1%～50% of a fatty acid ester quality, the dosage of organic solvent is 50%～300% of an amyl-based polyol quality, at first transesterification reaction is to carry out under 30 ℃～60 ℃, 200 rev/mins of 9KPa～42KPa vacuum tightnesss, temperature of reaction, and lasting 5h～30h; Then, under 1KPa～15KPa vacuum tightness, 30 ℃～60 ℃ temperature, distill out organic solvent; Secondly transesterification reaction is proceeded under 30 ℃～60 ℃, 200 rev/mins of 1KPa～15KPa vacuum tightnesss, temperature of reaction, continues 5h～30h again, the neopentyl polyol ester first product.
(2) separate: enzyme is separated from reaction product, again the neopentyl polyol ester first product is carried out molecular distillation, in the vacuum tightness less than 0.1Pa, temperature is under 150 ℃～200 ℃ the condition, steam excessive unreacted fatty acid ester, obtain the finished product neopentyl polyol ester.
Fatty acid ester RCOOR ' of the present invention, wherein R is the alkyl with 3～23 carbon atoms, and alkyl can be a straight or branched alkane, also can be saturated or unsaturated, and R ' is for having the alkyl of 1～2 carbon atom.
Amyl-based polyol of the present invention is represented by following structural:
Wherein R is selected from CH
3,-C
2H
5With-CH
2OH; Wherein not containing R is-CH
2OH.
Immobilized lipase of the present invention is the immobilized lipase Novozym 435 (being immobilized onto the macroporous acrylic resin) that derives from Candida antarctica.
Organic solvent of the present invention is the trimethyl carbinol.
Beneficial effect of the present invention: the present invention compares with the technology that adopts the chemical catalyst synthesis for polyol ester, have that reaction conditions gentleness, no coupling product, product are easy to collect,, non-pollutant discharge simple to equipment requirements, product color be shallow, the quality advantages of higher; The trimethyl carbinol is because its collateralization degree height, have 3 methyl, form bigger sterically hindered, difficult and fatty acid ester carries out transesterification reaction, and the trimethyl carbinol itself does not have toxicity to lipase, in reaction system, add the trimethyl carbinol, improved substrate solubleness, can make whole reaction system be homogeneous phase (except that immobilized enzyme), can also eliminate the negative impact of water fully to enzymatic activity and stability, improved reactive behavior and the stability of immobilized lipase Novozym 435, the yield of polyol ester is significantly improved.Fatty acid ester of the present invention can be from natural animal and plant grease and methyl alcohol or alcoholic acid alcoholysis product, and the main component of natural animal and plant grease is that glycerine and lipid acid (mainly are C
4～C
24Saturated or unsaturated acid) glyceryl ester that forms.Natural animal and plant grease source is abundant, cost is lower, is the recyclability resource.Deficient day by day along with the increasingly serious and petroleum resources of environmental problem, renewable resources is that raw material synthetic polyol ester has very big market potential to originate widely.
Embodiment
Below in conjunction with embodiment the novel technique scheme of a kind of synthesizing polyatomic alcohol ester by lipase catalysis of the present invention is further described.
The novel process of a kind of synthesizing polyatomic alcohol ester by lipase catalysis of the present invention comprises the steps:
(1) transesterification reaction: with mol ratio is that 2: 1～4.5: 1 fatty acid ester and amyl-based polyol joins in the Rotary Evaporators, and adding immobilized lipase and organic solvent, wherein the dosage of immobilized lipase is 1%～50% of a fatty acid ester quality, the dosage of organic solvent is 50%～400% of an amyl-based polyol quality, at first transesterification reaction is to carry out under 30 ℃～60 ℃, 200 rev/mins of 9KPa～42KPa vacuum tightnesss, temperature of reaction, and lasting 5h～35h; Then, under 1KPa～15KPa vacuum tightness, 30 ℃～60 ℃ temperature, distill out organic solvent; Secondly transesterification reaction is proceeded under 30 ℃～60 ℃, 200 rev/mins of 1KPa～15KPa vacuum tightnesss, temperature of reaction, continues 5h～35h again, the neopentyl polyol ester first product.
(2) separate: enzyme is separated from reaction product, again the neopentyl polyol ester first product is carried out molecular distillation, in the vacuum tightness less than 0.1Pa, temperature is under 150 ℃～200 ℃ the condition, steam excessive unreacted fatty acid ester, obtain the finished product neopentyl polyol ester.
Described fatty acid ester RCOOR ', wherein R is the alkyl with 3～23 carbon atoms, and alkyl can be a straight or branched alkane, also can be saturated or unsaturated, and R ' is for having the alkyl of 1～2 carbon atom.
Described amyl-based polyol is represented by following structural:
Wherein R is selected from CH
3,-C
2H
5With-CH
2OH; Wherein not containing R is-CH
2OH.
Described immobilized lipase is the immobilized lipase Novozym435 (being immobilized onto the macroporous acrylic resin) that derives from Candida antarctica.
Described organic solvent is the trimethyl carbinol.
Embodiment 1
With mol ratio is that 3.1: 1 Witconol 2301 and TriMethylolPropane(TMP) (13.57g) joins in the Rotary Evaporators, and the immobilized lipase Novozym 435 of adding Witconol 2301 quality 10%, and the trimethyl carbinol of TriMethylolPropane(TMP) quality 350%, transesterification reaction is at first carried out under 20KPa vacuum tightness, 40 ℃, 200 rev/mins, continues 8h; Then, under 5KPa vacuum tightness, 40 ℃ temperature, distill out the trimethyl carbinol; Secondly transesterification reaction is proceeded under 5KPa vacuum tightness, 40 ℃, 200 rev/mins, continues 24h again, and the tricarboxymethyl propane oleate yield is 95.8%.
Embodiment 2
With mol ratio is that 2.1: 1 Witconol 2301 and dimethyltrimethylene glycol (18.43g) joins in the Rotary Evaporators, and the immobilized lipase Novozym 435 of adding Witconol 2301 quality 10%, and the trimethyl carbinol of dimethyltrimethylene glycol quality 300%, transesterification reaction is at first carried out under 20KPa vacuum tightness, 40 ℃, 200 rev/mins, continues 8h; Then, under 5KPa vacuum tightness, 40 ℃ temperature, distill out the trimethyl carbinol; Secondly transesterification reaction is proceeded under 5KPa vacuum tightness, 40 ℃, 200 rev/mins, continues 20h again, and dimethyltrimethylene glycol oleic acid ester yield is 96.7%.
Embodiment 3
With mol ratio is that 3.5: 1 rapeseed methylester and TriMethylolPropane(TMP) (13.57g) joins in the Rotary Evaporators, and the immobilized lipase Novozym 435 of adding rapeseed methylester quality 10%, and the trimethyl carbinol of TriMethylolPropane(TMP) quality 300%, transesterification reaction is at first carried out under 20KPa vacuum tightness, 40 ℃, 200 rev/mins, continues 8h; Then, under 5KPa vacuum tightness, 40 ℃ temperature, distill out the trimethyl carbinol; Secondly transesterification reaction is proceeded under 5KPa vacuum tightness, 40 ℃, 200 rev/mins, continues 24h again, and TriMethylolPropane(TMP) rapeseed oil fatty acid ester yield is 92.3%.
The foregoing description only is used to illustrate.Various changes, substitutions and modifications beyond the embodiment of the invention are all in claims of the present invention within the claimed scope.
Claims (5)
1, a kind of novel process of synthesizing polyatomic alcohol ester by lipase catalysis is characterized in that this technology comprises:
(1) transesterification reaction: with mol ratio is that 2: 1～4.5: 1 fatty acid ester and amyl-based polyol joins in the Rotary Evaporators, and adding immobilized lipase and organic solvent, wherein the dosage of immobilized lipase is 1%～50% of a fatty acid ester quality, the dosage of organic solvent is 50%～400% of an amyl-based polyol quality, at first transesterification reaction is to carry out under 30 ℃～60 ℃, 200 rev/mins of 9KPa～42KPa vacuum tightnesss, temperature of reaction, and lasting 5h～35h; Then, under 1KPa～15KPa vacuum tightness, 30 ℃～60 ℃ temperature, distill out organic solvent; Secondly transesterification reaction is proceeded under 30 ℃～60 ℃, 200 rev/mins of 1KPa～15KPa vacuum tightnesss, temperature of reaction, continues 5h～35h again, the neopentyl polyol ester first product.
(2) separate: enzyme is separated from reaction product, again the neopentyl polyol ester first product is carried out molecular distillation, in the vacuum tightness less than 0.1Pa, temperature is under 150 ℃～200 ℃ the condition, steam excessive unreacted fatty acid ester, obtain the finished product neopentyl polyol ester.
2, according to the novel process of the described synthesizing polyatomic alcohol ester by lipase catalysis of claim 1, it is characterized in that: described fatty acid ester RCOOR ', wherein R is the alkyl with 3～23 carbon atoms, alkyl can be a straight or branched alkane, also can be saturated or unsaturated, R ' be for having the alkyl of 1～2 carbon atom.
3, according to the novel process of the described synthesizing polyatomic alcohol ester by lipase catalysis of claim 1, it is characterized in that: described amyl-based polyol is represented by following structural:
Wherein R is selected from CH
3,-C
2H
5With-CH
2OH; Wherein not containing R is-CH
2OH.
4, according to the novel process of the described synthesizing polyatomic alcohol ester by lipase catalysis of claim 1, it is characterized in that: described immobilized lipase is the immobilized lipase Novozym 435 that derives from Candida antarctica.
5, according to the novel process of the described synthesizing polyatomic alcohol ester by lipase catalysis of claim 1, it is characterized in that: described organic solvent is the trimethyl carbinol.
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