CN109096237A - A method of degradation high polymer procyanidine - Google Patents
A method of degradation high polymer procyanidine Download PDFInfo
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- CN109096237A CN109096237A CN201810929376.9A CN201810929376A CN109096237A CN 109096237 A CN109096237 A CN 109096237A CN 201810929376 A CN201810929376 A CN 201810929376A CN 109096237 A CN109096237 A CN 109096237A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/60—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2
- C07D311/62—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2 with oxygen atoms directly attached in position 3, e.g. anthocyanidins
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Abstract
The invention discloses a kind of methods of high polymer procyanidine of degrading, and belong to high polymer degradation technical field, including the use of ion liquid of quaternaries catalytic degradation high polymer procyanidine.The present invention has the advantages that ionic liquid dosage is few, reaction condition is mild, catalytic activity is high when utilizing ion liquid of quaternaries catalytic degradation high polymer procyanidine, it is complete to be catalyzed obtained oligomeric proanthocyanidins content height, molecular structure, and it is the preparation process simple process of ion liquid of quaternaries, at low cost, the ion liquid of quaternaries holding time being prepared is long, is suitble to industrial-scale production.
Description
Technical field
The present invention relates to the degradation of high polymer procyanidine, especially a kind of ionic liquid-catalyzed degradation high polymer original cyanine
The method of element, belongs to high polymer degradation technical field.
Background technique
Procyanidine (Proanthocyanidins, PC) is the total of the major class polyphenolic substance being widely present in plant
Claim, have the function of extremely strong anti-oxidant, elimination free radical, ultra-oxygen anion free radical and hydroxyl radical free radical can be effectively eliminated,
Phosphoric acid, arachidonic metabolism and protein phosphorylation are also assisted in, protects lipid that peroxide injury does not occur；It is strong
Metal-chelator, can chelated metal ions, form inert compound in vivo；Protection and stable vitamin c, facilitate vitamin
The absorption and utilization of c.Procyanidine is widely distributed, is present in skin, shell, seed, core, flower, the Ye Zhong of many plants, grape pip Central Plains
Anthocyanidin content highest, other such as pine bark, ginkgo leaf, fruit of glossy privet pericarps are also containing the procyanidine of different content.
Procyanidine is to be combined into structure by the catechin or epicatechin of different number.Simplest original cyanine
Element is catechin or epicatechin or catechin and the dimer that epicatechin is formed, and in addition there are tripolymer, tetramers etc.
Until ten aggressiveness etc..By the size of the degree of polymerization, two~pentamer is usually known as glucosidase procyanidins (abbreviation OPC), five are gathered
More than body it is known as high poly- procyanidine (abbreviation PPC).
Studies have shown that the connecting key and the degree of polymerization between the bioactivity and monomer composition, monomer of procyanidine are related.
Procyanidine two, three, the tetramer show good bioactivity, Central Plains in terms of inhibit in anti-oxidant, enzyme, is anti-
The activity of anthocyanidin dimer is best.The water solubility of glucosidase procyanidins preferably, can be used for water-soluble more demanding food
Product, drug and cosmetic industry.High poly- procyanidine poorly water-soluble, it is difficult to which be absorbed by the body utilization, and due to steric hindrance
It influences, the activity of phenolic hydroxyl group is affected, therefore major part can only be carried out as the low value-added byproduct such as natural pigment at present
It utilizes.However, most procyanidine in plant exist in the form of high polymer, in order to improve grape pip, pine bark, ginkgo leaf,
The bioactivity and water solubility of the extracts such as fruit of glossy privet pericarp, it is necessary to which high polymer procyanidine is degraded to oligomer original cyanine
Element.
Currently, the degradation of high polymer procyanidine mainly has oxidation degradation method, acid degradation method, alkaline bleach liquor degradation method and hydrogenation
Edman degradation Edman etc..As mentioned in patent document CN1654463A using hydrogen peroxide or potassium chlorate as oxidant degradation high polymer original flower
Green element, wherein hydrogen peroxide and potassium chlorate unstable, the easy decomposition in use and storage, thus cause catalytic efficiency low,
It expends larger, and easily causes procyanidine phenolic hydroxyl group to be oxidized to carboxyl product is caused to inactivate.Patent document CN101012216A
It is former to mention the high polymer extracted from grape pip etc. using acidic catalyst such as sulfuric acid, hydrochloric acid or highly acidic resin catalytic degradation
Anthocyanidin, no matter acid or alkaline bleach liquor degradation method, wherein used acid or alkali all can cause to corrode to equipment, discharge also can dirt
Environment is contaminated, and will lead to procyanidine molecular structure (especially biologically active phenolic hydroxyl group) and be destroyed, to reduce
The activity of procyanidine.A kind of side of hydrogenation degradation golden buckwheat high polymeric body procyanidine is mentioned in patent document CN101544703A
Method is carried out under inert atmosphere and high-pressure high-temperature environment, reacts more demanding, inconvenient.
Ionic liquid refers in room temperature or close to liquid, the salt as composed by zwitterion completely is presented at room temperature,
Referred to as low temperature molten salt.It is generally made of organic cation and inorganic or organic anion, and common cation has quaternary ammonium salt
Ion, quaternary phosphine salt ion, imidazolium ion and pyrroles's salt ion etc., anion has halide ion, tetrafluoroborate ion, hexafluoro
Phosphate anion etc..According to the difference of organic cation parent in ionic liquid, ionic liquid can be divided into imidazole salt, pyrrole
Pyridine salt, quaternary ammonium salt and quaternary phosphonium salt class etc.；It, can also be by ionic liquid point according to ionic liquid deliquescent difference in water
For hydrophilic ionic-liquid and hydrophobic ionic liquid.
The significant difference of ionic liquid and traditional fuse salt is that its fusing point is relatively low, generally below 150 DEG C, according to from
This property of sub- liquid can use it to replace traditional organic solvent and electrolyte as chemical reaction and electrochemical system
Medium etc..The features such as unique adjustable electrostatic field of ionic liquid, special ionic environment and multidimensional weak interaction, makes people
More easily catalytic reaction activity and selectivity are regulated and controled using effective means.The low volatilization of ionic liquid and low combustible etc.
Property keeps its catalysis reaction safer, so, when ionic liquid is used as reaction medium or catalyst, or have both simultaneously above-mentioned
When two kinds of effects, tend to show special catalytic performance.Ionic liquid also has many conventional solvents incomparable
Advantage, such as high thermal stability, insignificant vapour pressure, wide liquid temperature section, regulatable to polarity and apolar substance
Good solubility, designability, nontoxic, easy recycling and can be as green solvent applied to organic and polymer substance synthesis
Or degradation etc., ionic liquid also have and can substitute conventional organic solvents medium and chemically reacted (especially catalysis reaction),
To realize the greenization of reaction process, therefore the research of ionic liquid has obtained swift and violent development.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of methods of high polymer procyanidine of degrading, and can use quaternary ammonium
High polymer procyanidine is degraded to oligomeric proanthocyanidins by salt ion liquid, solves the catalyst such as soda acid to oligomer original cyanine
The destructive high problem of plain molecular structure, and reduce the dosage of catalyst, extend the activity-maintaining time of catalyst.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A method of degradation high polymer procyanidine utilizes ion liquid of quaternaries catalytic degradation high polymer original cyanine
Element.
Technical solution of the present invention further improvement lies in that: by ion liquid of quaternaries, high polymer procyanidine mix
After be heated to 15~35 DEG C, be stirred to react 0.5~2.5 hour.
Technical solution of the present invention further improvement lies in that: the high polymer procyanidine derive from grape pip extraction
Object, the content of extract procyanidins are 75~95%, and the degree of polymerization is 8~12.
Technical solution of the present invention further improvement lies in that: 1.8~2.2 milliliters of quaternary ammonium salts of every gram of high polymer procyanidine
The ionic liquid-catalyzed degradation of class, the concentration of ion liquid of quaternaries are 0.8~1.5mg/mL.
Technical solution of the present invention further improvement lies in that the preparation step of ion liquid of quaternaries is as follows:
A. it is heated to 60~70 DEG C after 1,3-propane sultone being mixed with ethyl acetate, is slowly added to quaternary ammonium while stirring
Salt is cooled to room temperature after reacting 2~3h, then isolated solid product；
B. deionized water is added into solid product, is warming up to 95~105 DEG C, anhydrous p-aminobenzene sulfonic acid is then added,
It is cooled to room temperature after stirring to complete liquefaction.
Technical solution of the present invention further improvement lies in that: in the step A quaternary ammonium salt be N, N- dimethyl butylamine, N, N-
Dimethyl n octylame, N, any one of N- dimethyl dodecylamine or N, N- dimethyl tetradecyl amine.
Technical solution of the present invention further improvement lies in that: in the step A quaternary ammonium salt be N, N- dimethyl tetradecyl base
Amine.
Technical solution of the present invention further improvement lies in that: 1,3- propane sultone and quaternary ammonium salt rubs in the step A
, than being 1:1~1.5, the volume of ethyl acetate used is 4~6 times of 1,3-propane sultone and quaternary ammonium salt total volume for you.
Technical solution of the present invention further improvement lies in that: 1~1.5 milli is added in every milligram of solid product in the step B
The molar ratio of liter deionized water, solid product and anhydrous p-aminobenzene sulfonic acid is 1:0.8~1.2.
Technical solution of the present invention further improvement lies in that: in the step A separate solid product when using filter, then
It is washed 2~4 times with ethyl acetate, then is dried in vacuo 2~3h at 95~105 DEG C.
By adopting the above-described technical solution, the technological progress achieved by the present invention is:
The present invention provides a kind of method using ion liquid of quaternaries degradation high polymer procyanidine, quaternary ammonium salts
With ionic liquid dosage is few, reaction condition is mild, catalytic activity is high when ionic liquid-catalyzed degradation high polymer procyanidine
Advantage, the oligomeric proanthocyanidins content being catalyzed is high, molecular structure is complete, and the preparation of ion liquid of quaternaries
Journey simple process, at low cost, the ion liquid of quaternaries holding time being prepared is long, is suitble to industrial-scale production.
The degradable high polymer procyanidine extracted from grape pip of ion liquid of quaternaries of the invention, wherein
The content of the average high polymer procyanidine in 8~12, extract of the high polymer procyanidine degree of polymerization is 75~95%, is utilized
The high polymer procyanidine in these sources can be degraded to oligomeric proanthocyanidins by ion liquid of quaternaries of the invention, degradation
Rate can reach 50~70%.
Few with ionic liquid dosage when the present invention utilizes ion liquid of quaternaries catalytic degradation high polymer procyanidine,
The advantage that catalytic activity is high and reaction condition is mild.Ion liquid of quaternaries is used to degrade high polymer procyanidine by the present invention
When, every gram of high polymer procyanidine only needs the quaternary ammonium salt ionic liquid that 1.8~2.2 milliliters of concentration is 0.8~1.5mg/mL
High polymer procyanidine can be degraded to oligomeric proanthocyanidins by body, compared with tradition is degraded using acid or base catalysis, catalysis
Ion liquid of quaternaries is fewer than acid or alkali needed for the high polymer procyanidine catalysis of degradation identical weight uses more than ten or even several
Ten times；Catalytic degradation of the present invention is carried out under 15~35 DEG C of cryogenic conditions, and temperature is low, and low energy consumption, with acidic catalyst and
Base catalysis is compared, non-corrosive to consersion unit, and without special consersion unit, reaction condition is mild；With oxidation degradation method
It compares, ion liquid of quaternaries has that stability is strong, is not easily decomposed, the advantage that catalytic activity is stable；With hydrogenation edman degradation Edman phase
Than being not necessarily to high temperature and pressure, required cost of degrading is low, is suitble to industrial-scale production；In addition, quaternary ammonium salt ion of the invention
Liquid easily recycles, and may be recovered using the methods of conventional distillation or extraction, recovery method is simple and effective, not will cause ring
Border pollution.
The high catalytic efficiency of ion liquid of quaternaries of the invention, cryogenic conditions, suitable stirring with 15~35 DEG C
Speed and catalysis time match, and the oligomeric proanthocyanidins molecular structure made is complete, and active phenolic hydroxyl group will not be by
Destroy, and the higher dimer procyanidin content of antioxidant activity is higher, obtained oligomeric proanthocyanidins it is anti-oxidant,
Enzyme inhibition, anti-mutation etc. have good bioactivity.
Raw material type needed for the preparation of ion liquid of quaternaries of the present invention is few, proportion is reasonable, activity is high.Quaternary ammonium of the present invention
Salt ion liquid is only by 1,3- propane sultone, ethyl acetate, quaternary ammonium salt, deionized water and this is several to anhydrous aminobenzenesulfonic acid
Kind, required raw material type is few；Carrying out certain reaction by certain molar ratio between each substance can be prepared by quaternary ammonium salt ion
Liquid；By the ion liquid of quaternaries that 1.8~2.2 milliliters are added in every gram of high polymer procyanidine, quaternary ammonium salt ionic liquid
Body can be such that the connecting key between high polymer procyanidine each unit is broken, anhydrous p-aminobenzene sulfonic acid in quaternary ammonium salt ionic liquid
Addition so that high polymer procyanidine is in sourer environment, promote the solution of each polymerized unit of high polymer procyanidine
From enhancing the catalytic activity of ion liquid of quaternaries, can drop high polymer procyanidine therein in 0.5~2.5h
Solution is oligomeric proanthocyanidins, and dimer procyanidin content is high in obtained oligomeric proanthocyanidins.
Ion liquid of quaternaries preparation process used in present invention degradation high polymer procyanidine is simple.Quaternary ammonium of the present invention
Each reaction raw materials need to be only stirred reaction by salt ion liquid under the conditions ofs certain temperature etc. when preparing, filtering is added an examination of again
Agent dissolution can be prepared by, and step is simple, and required each raw material is the conventional medication of chemical field, without special
Equipment, it is at low cost.
The present invention degrades ion liquid of quaternaries preparation process used in high polymer procyanidine can be by preparation process
Obtained in solid washing of precipitate and be sealed after drying, then added when catalytic degradation high polymer procyanidine
Ionized water and anhydrous p-aminobenzene sulfonic acid.Solid precipitating therein, which saves, to be more convenient, and is put in hermetic bag and is sealed,
In subsequent use according to dosage measure appropriate quality solid precipitating can be configured to ion liquid of quaternaries, be easy to use and
Storage or transport；In addition, the long shelf-life of ion liquid of quaternaries, is sealed at normal temperature, preservation condition is simple,
It saves at low cost.
Specific embodiment
The present invention is described in further details below with reference to embodiment:
A method of degradation high polymer procyanidine carries out catalytic degradation using ion liquid of quaternaries.It is wherein high
Aggressiveness procyanidine derives from the extract of grape pip, and the degree of polymerization of high polymer procyanidine is 8~12 in extract, former cyanine
The content of element is 75~95%.
Ion liquid of quaternaries is first prepared, the preparation method is as follows:
First 1,3-propane sultone, ethyl acetate and quaternary ammonium salt are added in reaction vessel, wherein 1,3-propane sultone
Molar ratio with quaternary ammonium salt is 1:1~1.5, and the additional amount of ethyl acetate is calculated by volume as 1,3- propane sultone and quaternary ammonium salt
1,3-propane sultone, ethyl acetate are preferably first added to reaction and held by 4~6 times of total volume, the adding manner of three kinds of substances
In device, then quaternary ammonium salt is slowly added to by constant pressure funnel, is stirred while quaternary ammonium salt is added dropwise；Three kinds of substances are equal
2~3h (white precipitate generation is had during reaction) is stirred to react after being added in reaction vessel under the conditions of 60~70 DEG C,
It is cooled to room temperature after reaction, then is filtered to obtain solid precipitating；Obtained solid precipitating is washed with ethyl acetate
It washs, washs every milligram of solid precipitating every time and washed with 3~5 milliliters of ethyl acetate, washing times are 2~4 times；Then will
Solid precipitating after washing is dried, and using vacuum oven, (what is obtained is dry by dry 2~3h at 95~105 DEG C when dry
Solid after dry precipitates salable preservation, after then taking appropriate solid precipitating to carry out again in catalytic degradation high polymer procyanidine
Continuous preparation process)；Deionized water (consolidating after every milligram of drying finally is added into the solid precipitating (solid product) after drying
1~1.5 milliliter of deionized water is added in body precipitating), anhydrous p-aminobenzene sulfonic acid is added when being warming up to 95~105 DEG C, after dry
Solid precipitating and the molar ratio of anhydrous p-aminobenzene sulfonic acid be 1:0.8~1.2, stirring to solid precipitates cooling after liquefaction completely
To room temperature to get arrive ionic liquid of the invention；Wherein quaternary ammonium salt be N, N- dimethyl butylamine, N, N- dimethyl n octylame, N,
N- dimethyl dodecylamine or N, any one of N- dimethyl tetradecyl amine, preferably N, N- dimethyl tetradecyl amine.
The concentration of the ionic liquid prepared is 0.8~1.5mg/ml, and ionic liquid can be sealed at normal temperature, guarantee the quality
Phase is 6~8 months.
By the ionic liquid of above-mentioned preparation be used to degrade high polymer procyanidine when the step of it is as follows: by high polymer original cyanine
Element, ionic liquid press 1000:1.8~2.2, and the mass volume ratio that unit is mg/ml is added in reaction vessel, it is again heated to 15~
35 DEG C, 0.5~2.5h of lower reaction is sufficiently stirred.
Embodiment 1
Quaternary ammonium salt ionic liquid-C4 ionic liquid, the preparation method is as follows:
1,3-propane sultone, N are first weighed, the molar ratio of N- dimethyl butylamine, two kinds of substances is 0.8:1, then weighs 1,
First reaction is added in 1,3-propane sultone, ethyl acetate by 4 times of ethyl acetate of 3-N-morpholinopropanesulfonic acid lactone and quaternary ammonium salt total volume
In container, then by constant pressure funnel by N, N- dimethyl butylamine is slowly added in reaction vessel, while quaternary ammonium salt is added dropwise
It is stirred；Three kinds of substances are stirred to react 2h after being added in reaction vessel under the conditions of 60 DEG C and (have during reaction white
Color precipitating generates), it is cooled to room temperature after reaction, then filtered to obtain solid precipitating；The solid precipitating second that will be obtained
Acetoacetic ester is washed, and is washed every milligram of solid precipitating every time and is washed with 3 milliliters of ethyl acetate, washing times are 4 times；
Then the solid precipitating after washing is dried, it is dry (big to being completely dried at 95 DEG C using vacuum oven when dry
Dry 2h is about needed, the solid after obtained drying precipitates salable preservation, then again in catalytic degradation high polymer procyanidine
Appropriate solid precipitating is taken to carry out subsequent preparation process)；Finally (every milligram of deionized water is added into the solid precipitating after drying
1 milliliter of deionized water is added in solid precipitating after drying), anhydrous p-aminobenzene sulfonic acid is added when being warming up to 95 DEG C, after dry
Solid precipitating and the molar ratio of anhydrous p-aminobenzene sulfonic acid be 1:0.8, stirring to solid is cooled to room after precipitating liquefaction completely
Temperature to get arrive C4 ionic liquid of the invention.
By the ionic liquid of above-mentioned preparation be used to degrade high polymer procyanidine when the step of it is as follows: by high polymer original cyanine
Element, C4 ionic liquid press 1000:1.8, and the mass volume ratio that unit is mg/ml is added in reaction vessel, is again heated to 35 DEG C, fills
Divide stirring is lower to react 2.5h, the average degree of polymerization before and after sampling analysis measuring hydrolysis, average degree of polymerization is 7, after hydrolysis before hydrolyzing
Product average degree of polymerization is 3.5.
Embodiment 2
Quaternary ammonium salt ionic liquid-C8 ionic liquid, the preparation method is as follows:
1,3-propane sultone, N are first weighed, the molar ratio of N- dimethyl n octylame, two kinds of substances is 1:1, then weighs 1,
First reaction is added in 1,3-propane sultone, ethyl acetate by 5 times of ethyl acetate of 3-N-morpholinopropanesulfonic acid lactone and quaternary ammonium salt total volume
In container, then by constant pressure funnel by N, N- dimethyl n octylame is slowly added in reaction vessel, and the same of quaternary ammonium salt is added dropwise
When be stirred；Three kinds of substances are stirred to react 2.5h (meeting during reaction under the conditions of 65 DEG C after being added in reaction vessel
Have white precipitate generation), it is cooled to room temperature after reaction, then filtered to obtain solid precipitating；Obtained solid is precipitated
It is washed with ethyl acetate, washs every milligram of solid precipitating every time and washed with 4 milliliters of ethyl acetate, washing times are
3 times；Then the solid precipitating after washing is dried, is dried at 100 DEG C to completely dry when dry using vacuum oven
It is dry (about to need dry 2.5h, the solid after obtained drying precipitates salable preservation, then in catalytic degradation high polymer original cyanine
Appropriate solid precipitating is taken to carry out subsequent preparation process when plain again)；Deionized water finally is added into the solid precipitating after drying
(1.2 milliliters of deionized water is added in the solid precipitating after every milligram of drying), is added anhydrous p-aminophenyl sulphur when being warming up to 100 DEG C
Acid, the molar ratio of solid precipitating and anhydrous p-aminobenzene sulfonic acid after drying is 1:1, cold after stirring to solid precipitating liquefaction completely
But to room temperature to get arrive C8 ionic liquid of the invention.
By the ionic liquid of above-mentioned preparation be used to degrade high polymer procyanidine when the step of it is as follows: by high polymer original cyanine
Element, C8 ionic liquid press 100:2.2, and the mass volume ratio that unit is mg/ml is added in reaction vessel, is again heated to 15 DEG C, fills
Divide stirring is lower to react 2h；The average degree of polymerization of sampling analysis measuring hydrolysis front and back, average degree of polymerization is 8 before hydrolyzing, and is produced after hydrolysis
Object average degree of polymerization is 3.6.
Embodiment 3
Quaternary ammonium salt ionic liquid-C12 ionic liquid, the preparation method is as follows:
1,3-propane sultone, N, N- dimethyl dodecylamine are first weighed, the molar ratio of two kinds of substances is 1.2:1, then
6 times of ethyl acetate for weighing 1,3-propane sultone and quaternary ammonium salt total volume, first adds 1,3-propane sultone, ethyl acetate
Enter in reaction vessel, then by constant pressure funnel by N, N- dimethyl dodecylamine is slowly added in reaction vessel, is added dropwise
It is stirred while quaternary ammonium salt；Three kinds of substances be stirred to react under the conditions of 70 DEG C after being added in reaction vessel 3h (reaction
White precipitate generation is had in the process), it is cooled to room temperature after reaction, then filtered to obtain solid precipitating；By what is obtained
Solid precipitating is washed with ethyl acetate, is washed every milligram of solid precipitating every time and is washed with 5 milliliters of ethyl acetate, is washed
Washing number is 2 times；Then the solid precipitating after washing is dried, it is dry at 105 DEG C using vacuum oven when dry
(dry 3h is about needed, the solid after obtained drying precipitates salable preservation, then in catalytic degradation high polymer to being completely dried
Appropriate solid precipitating is taken to carry out subsequent preparation process when procyanidine again)；It is finally added and goes into the solid precipitating after drying
Ionized water (1.5 milliliters of deionized water is added in the solid precipitating after every milligram of drying), is added anhydrous to ammonia when being warming up to 105 DEG C
The molar ratio of base benzene sulfonic acid, solid precipitating and anhydrous p-aminobenzene sulfonic acid after drying is 1:1.2, and stirring to solid precipitates complete
It is cooled to room temperature after liquefaction to get C12 ionic liquid of the invention is arrived.
By the ionic liquid of above-mentioned preparation be used to degrade high polymer procyanidine when the step of it is as follows: by high polymer original cyanine
Element, C12 ionic liquid press 1000:2, and the mass volume ratio that unit is mg/ml is added in reaction vessel, is again heated to 20 DEG C, fills
Divide stirring is lower to react 1h；The average degree of polymerization of sampling analysis measuring hydrolysis front and back, average degree of polymerization is 7 before hydrolyzing, and is produced after hydrolysis
Object average degree of polymerization is 2.9.
Embodiment 4
Quaternary ammonium salt ionic liquid-C14 ionic liquid, the preparation method is as follows:
1,3-propane sultone, N are first weighed, the molar ratio of N- dimethyl tetradecyl amine, two kinds of substances is 1:1, then is claimed
5 times of ethyl acetate of 1,3-propane sultone and quaternary ammonium salt total volume is taken, first 1,3-propane sultone, ethyl acetate are added
In reaction vessel, then by constant pressure funnel by N, N- dimethyl tetradecyl amine is slowly added in reaction vessel, and season is added dropwise
It is stirred while ammonium salt；Three kinds of substances be stirred to react under the conditions of 65 DEG C after being added in reaction vessel 2.5h (reaction
White precipitate generation is had in the process), it is cooled to room temperature after reaction, then filtered to obtain solid precipitating；By what is obtained
Solid precipitating is washed with ethyl acetate, is washed every milligram of solid precipitating every time and is washed with 5 milliliters of ethyl acetate, is washed
Washing number is 3 times；Then the solid precipitating after washing is dried, it is dry at 100 DEG C using vacuum oven when dry
(dry 2h is about needed, the solid after obtained drying precipitates salable preservation, then in catalytic degradation high polymer to being completely dried
Appropriate solid precipitating is taken to carry out subsequent preparation process when procyanidine again)；It is finally added and goes into the solid precipitating after drying
Ionized water (1 milliliter of deionized water is added in the solid precipitating after every milligram of drying), is added anhydrous to amino when being warming up to 100 DEG C
Benzene sulfonic acid, the molar ratio of solid precipitating and anhydrous p-aminobenzene sulfonic acid after drying are 1:1, stirring to solid precipitating liquefaction completely
It is cooled to room temperature afterwards to get C14 ionic liquid of the invention is arrived.
By the ionic liquid of above-mentioned preparation be used to degrade high polymer procyanidine when the step of it is as follows: by high polymer original cyanine
Element, C14 ionic liquid press 1000:1.8, and the mass volume ratio that unit is mg/ml is added in reaction vessel, are again heated to 35 DEG C,
Lower reaction 0.5h is sufficiently stirred；The average degree of polymerization of sampling analysis measuring hydrolysis front and back, average degree of polymerization is 8 before hydrolyzing, hydrolysis
Product average degree of polymerization is 3.4 afterwards.
Embodiment 5
Advantage to illustrate the invention, ion liquid of quaternaries degradation high polymer original cyanine prepared by embodiment 1 to 3
Element, using the mass concentration of traditional vanillin method measurement procyanidine, the high polymer procyanidine source of degradation is all the same, dosage
For 0.5g, degradation temperature is 25 DEG C, and ion liquid of quaternaries dosage prepared by the used embodiment of the present invention 1 to 4 is 1ml,
Specific test process is as follows:
4 clean 100ml flasks are taken, 0.5g high polymer procyanidine is separately added into, then are separately added into 4 kinds of above-mentioned seasons
Ammonium salt class ionic liquid, sulfurous acid and sodium hydroxide；Flask is installed on water-bath magnetic stirring apparatus, magnetic agitation is opened,
Set temperature is 25 DEG C, keeps this temperature to open stirring, takes respectively when reacting 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h
Sample, every 100 μ l of sub-sampling；It opens ultraviolet specrophotometer to be preheated, spectrophotometer is configured, model selection is to inhale
Luminosity, wavelength selection 500nm, and instrument is calibrated, by no color developing agent that response sample is added, (hydrochloric acid vanillic aldehyde is mixed
Close solution) it is added in cuvette, cuvette is placed into spectrophotometer, can carry out sample inspection after deducting blank interference
It surveys；The sample of taking-up is added in the 10ml colorimetric cylinder containing 6ml color developing agent, plug is covered, sufficiently shakes up, be put into shady place
It is protected from light 5min；After the reaction was completed, it is transferred in cuvette, cuvette is placed into spectrophotometer and is detected, examine
It is as follows to survey result, wherein (procyanidine has maximum absorbance value to reaction system in 500nm after absorbance i.e. reaction different time
Wavelength) at absorbance value, concentration be reaction system procyanidins content, unit be μ l/ml, specific targets such as following table
It is shown:
Table 1
The ionic liquid-catalyzed effect of C14 is best as can be seen from Table 1, and maximum absorbance numerical value is 0.730, corresponding original cyanine
Plain concentration is 40.042 μ l/ml.Experiment display ionic-liquid catalyst has certain when being catalyzed the hydrolysis of high polymer procyanidine
Fluctuation.The reason is that procyanidine can be changed into anthocyanidin under strongly acidic conditions, but reaction proceeds to oligomeric original when 2.0h
Anthocyanin concentrations reach peak value, and degradation effect is best.
Though the oligomeric proanthocyanidins that ion liquid of quaternaries catalytic degradation obtains are than sulfurous acid and sodium hydroxide catalyzed
Obtained oligomeric proanthocyanidins content of degrading is low, but either sulfurous acid or sodium hydroxide catalyzed degradation high polymer original flower
Green element all has certain corrosiveness to consersion unit, and ion liquid of quaternaries is utilized then will not to generate corruption to consersion unit
Erosion effect, extends the service life of consersion unit.
Claims (10)
1. a kind of method for high polymer procyanidine of degrading, it is characterised in that: high using ion liquid of quaternaries catalytic degradation
Aggressiveness procyanidine.
2. it is according to claim 1 it is a kind of degrade high polymer procyanidine method, it is characterised in that: by quaternary ammonium salt from
15~35 DEG C are heated to after sub- liquid, the mixing of high polymer procyanidine, is stirred to react 0.5~2.5 hour.
3. a kind of method of high polymer procyanidine of degrading according to claim 2, it is characterised in that: the high polymer is former
Anthocyanidin derives from the extract of grape pip, and the content of extract procyanidins is 75~95%, and the degree of polymerization is 8~12.
4. a kind of method of high polymer procyanidine of degrading according to claim 2, it is characterised in that: every gram of high polymer original
1.8~2.2 milliliters of ion liquid of quaternaries catalytic degradations of anthocyanidin, the concentration of ion liquid of quaternaries is 0.8~
1.5mg/mL。
5. a kind of method of high polymer procyanidine of degrading according to any one of claims 1 to 4, it is characterised in that quaternary ammonium
The preparation step of salt ion liquid is as follows:
A. it is heated to 60~70 DEG C after 1,3-propane sultone being mixed with ethyl acetate, is slowly added to quaternary ammonium salt while stirring,
It is cooled to room temperature after 2~3h of reaction, then isolated solid product；
B. deionized water is added into solid product, is warming up to 95~105 DEG C, anhydrous p-aminobenzene sulfonic acid is then added, stirs
It is cooled to room temperature after to complete liquefaction.
6. a kind of method of high polymer procyanidine of degrading according to claim 5, it is characterised in that: in the step A
Quaternary ammonium salt is N, N- dimethyl butylamine, N, N- dimethyl n octylame, N, N- dimethyl dodecylamine or N, N- dimethyl 14
Any one of alkylamine.
7. a kind of method of high polymer procyanidine of degrading according to claim 6, it is characterised in that: in the step A
Quaternary ammonium salt is N, N- dimethyl tetradecyl amine.
8. a kind of method of high polymer procyanidine of degrading according to claim 5, it is characterised in that: in the step A
1,3-propane sultone and the molar ratio of quaternary ammonium salt are 1:1~1.5, the volume of ethyl acetate used be 1,3-propane sultone and
4~6 times of quaternary ammonium salt total volume.
9. a kind of method of high polymer procyanidine of degrading according to claim 5, it is characterised in that: in the step B
1~1.5 ml deionized water is added in every milligram of solid product, and the molar ratio of solid product and anhydrous p-aminobenzene sulfonic acid is 1:
0.8~1.2.
10. a kind of method of high polymer procyanidine of degrading according to claim 5, it is characterised in that: in the step A
It using filtering when separating solid product, is then washed 2~4 times with ethyl acetate, then is dried in vacuo 2~3h at 95~105 DEG C.
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| CN113321635A (en) * | 2021-04-21 | 2021-08-31 | 东北林业大学 | Hydrogenolysis method of high polymeric proanthocyanidins, product and application thereof |
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| CN1654463A (en) * | 2004-02-13 | 2005-08-17 | 杭州利欣生物科技有限公司 | Procyanidins oligomer and its preparing method and use |
| EP1826203A1 (en) * | 2004-11-17 | 2007-08-29 | Toyo Shinyaku Co., Ltd. | Composition containing flavan compound |
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| CN1654463A (en) * | 2004-02-13 | 2005-08-17 | 杭州利欣生物科技有限公司 | Procyanidins oligomer and its preparing method and use |
| EP1826203A1 (en) * | 2004-11-17 | 2007-08-29 | Toyo Shinyaku Co., Ltd. | Composition containing flavan compound |
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