CN108727515A - The chitosan-based polyalcohol of vegetable oil acid-is catalyzed the method for preparing the polyalcohol with free radical photo-initiation - Google Patents
The chitosan-based polyalcohol of vegetable oil acid-is catalyzed the method for preparing the polyalcohol with free radical photo-initiation Download PDFInfo
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- CN108727515A CN108727515A CN201810645617.7A CN201810645617A CN108727515A CN 108727515 A CN108727515 A CN 108727515A CN 201810645617 A CN201810645617 A CN 201810645617A CN 108727515 A CN108727515 A CN 108727515A
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- chitosan
- vegetable oil
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- oil acid
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 152
- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 77
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- 238000000034 method Methods 0.000 title claims description 13
- 150000003254 radicals Chemical class 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 48
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 47
- 229920001577 copolymer Polymers 0.000 claims description 38
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 36
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 24
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 13
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- 238000006555 catalytic reaction Methods 0.000 claims description 4
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- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical class C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 2
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 claims description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention discloses a kind of chitosan-based polyalcohol of vegetable oil acid-, shown in structural formula such as formula (I)：Wherein, n, k=0 or 1,0 < m+s <, 4,12 < h+m+n+s+t < 16；R is C1~C4 straight chains or linear paraffin base.The invention also discloses the preparation method and applications of the chitosan-based polyalcohol of above-mentioned vegetable oil acid-.The present invention is reacted for substrate material using mercaptan-alkene clicking chemistry so that vegetable oil acid-is chitosan-based, and ester exchange reaction is carried out with polyunsaturated vegetable oil acid fat by the amino in chitosan；Then the click-reaction by the double bond on sulfydryl and vegetable oil long-chain under ultraviolet light, introduce long-chain, C-S keys, prepare vegetable oil acid-chitosan polyalcohol, plasticity, the antibiotic property of chitosan can not only be utilized, and the flexibility of polyunsaturated vegetable oil fat long-chain can be utilized, prepare multifunctional groups biomass polyalcohol.
Description
Technical field
The invention belongs to UV photocatalysis technologies fields, and in particular to a kind of chitosan-based polyalcohol of vegetable oil acid-further relates to
The method for preparing the chitosan-based polyalcohol of vegetable oil acid-with free radical photo-initiation catalysis.
Background technology
It is well known that the non-renewable fossil resource such as oil and natural gas constitutes world today's fuel and chemical industry
Foundation stone.Traditional polyols preparation raw material multi-source is in resources such as oil and natural gas, with the day of the resources such as oil, natural gas
Gradually the enhancing of shortage and people's environmental consciousness, the research of biomass polyalcohol are concerned by people more and more.Biomass
As renewable resource, source is very extensive, and oil can be not only substituted in terms of the energy with polyalcohol prepared by biomass
Matter polyalcohol alleviates oil and natural gas increasingly crisis in short supply, but also can synthesize numerous chemicals or chemistry is intermediate
Body has irreplaceable effect in environmental protection and in terms of overcoming energy crisis.Therefore, Developing Biomass polyalcohol will become the world
The important trend of the energy and chemical industry.
The main component of vegetable oil is the unsaturated fatty acids such as fatty glyceride, carboxyl, ester group and not from structure
The double bond of saturated fatty acid can introduce hydroxyl by certain reaction, generally by epoxidation or ozonation treatment,
Then hydroxylating being carried out with the compound of the active hydrogen such as alcohol or acid under the action of catalyst and introducing hydroxyl, preparing has
The polyalcohol of certain functional group and relative molecular mass.
Chitosan is cellulose to be only second in nature and a large amount of existing high-molecular compounds, due on its molecular structure
Polar functional group with a large amount of amino, hydroxyl, make it have good biodegradable, biocompatibility, biocidal property with
And the features such as film forming.In addition, amino and hydroxyl also give the stronger reactivity of chitosan molecule, be easy to happen hydrolysis,
The chemical reactions such as alkylation, acylation, carboxy methylation, sulfonation, nitrification, halogenation, oxidation, reduction, condensation and complexing produce each
Chitosan derivatives of the kind with different performance.
Mercaptan-alkene clicking chemistry and mercaptan-alkynes click chemistry and referred to as mercaptan-alkene/alkynes click chemistry.Click chemistry reacts
Have many advantages, such as that reaction condition is mild, yield is high, rate is fast, product can be easily separated and high selectivity, a system can be utilized
Row high efficient and reliable and selective C-S binding reactions realize that atom connects, and carry out novel high-performance and functional polymer
Modularization prepare.
In the prior art, patent CN105669450A disclose a kind of high hydroxyl value plant oil polyhydric alcohol and preparation method thereof with
Ring-opening reaction occurred by epoxidized vegetable oil and polyol using, the invention and ester exchange reaction that vegetable oil is prepared is more
First alcohol；
Patent CN105669450A discloses a kind of using method for oxidation novel polyols derived from vegetable oil, the invention
It provides a kind of by making vegetable oil be produced with increased hydroxyl with oxidant reaction in the presence of organo-metallic catalyst
The method of polyalcohol derived from the vegetable oil of base degree of functionality；
Patent CN103274930A discloses a kind of method preparing vegetable oil polyol using continuity method, which provides
The preparation method of vegetable oil polyol be continuous operation, epoxidation and open loop two-step reaction are combined into a step in the process, had
The feature that preparation process is simple and easy to control, safe, the reaction time is short, low energy consumption, pollution is small.
The disclosed technology of the above invention is that vegetable oil-based polyols are prepared using vegetable oil as substrate modified, is not carried
And chitosan-based polyalcohol of vegetable oil acid-and preparation method thereof, especially by after vegetable oil acid and chitosan reaction product with
The method that mercaptan prepares the chitosan-based polyalcohol of vegetable oil acid-under conditions of ultraviolet light by click-reaction, and this skill
Art is rarely reported.
Therefore, it is quite necessary to a kind of chitosan-based polyalcohol of vegetable oil acid-be developed, to enrich biomass polyalcohol
Type, and make biomass polyalcohol multifunction.
Invention content
The purpose of the present invention is to provide a kind of chitosan-based polyalcohol of vegetable oil acid-, with one in solving the above problems
It is a or multiple.
Another object of the present invention is also resided in a kind of be catalyzed with free radical photo-initiation of offer and prepares above-mentioned vegetable oil acid-
The method of chitosan-based polyalcohol, one or more of to solve the above problems.
According to an aspect of the invention, there is provided a kind of chitosan-based polyalcohol of vegetable oil acid-, structural formula such as formula
(I) shown in：
Wherein, n, k=0 or 1,0 < m+s <, 4,12 < h+m+n+s+t < 16；
R is C1~C4 straight chains or linear paraffin base.
According to an aspect of the invention, there is provided preparing the preparation side of above-mentioned polyalcohol with free radical photo-initiation catalysis
Method is as follows：
Chitosan graft vegetable oil acid copolymer (as shown in formula (II)) is mixed with mercaptan, free radical photo-initiation,
Under the irradiation of UV light, reaction is carried out at the same time magnetic agitation, then with the first organic solvent diluting, is washed through supersaturated inorganic salt solution
Afterwards, drying processing, filtering are placed in vacuum drying chamber finally by Rotary Evaporators the first organic solvent of removing and do
It is dry, it obtains causing the chitosan-based polyalcohol of vegetable oil acid-synthesized by free radical photo-initiation (as shown in formula (I)).
Wherein, the synthetic reaction of the chitosan-based polyalcohol of above-mentioned vegetable oil acid-is as follows：
Wherein, n, k=0 or 1,0 < m+s <, 4,12 < h+m+n+s+t < 16.
In some embodiments, vegetable oil acid be ricinoleic acid, eleostearic acid, linolenic acid, linoleic acid, in oleic acid extremely
Few one kind.
In some embodiments, mercaptan is 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 2,3- dimercaprol dimercaptopropanol, 1- mercaptos
In base -2- propyl alcohol, 2- sulfydryl -3- propyl alcohol, 6- sulfydryl hex- 1- alcohol, 3- sulfydryl -2- butanol, 11- sulfydryl -1- undecyl alcohols at least
It is a kind of.
In some embodiments, free radical photo-initiation is 2- hydroxy-2-methyl -1- phenylacetone (trade names
1173), 1- hydroxycyclohexyl phenyl ketones (trade name 184), 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) benzene
Base] -1- acetone (trade name 907), 2,4,6- trimethylbenzoy-dipheny phosphine oxides (trade name TPO), 2,4,6-
Trimethylbenzoyl phenyl phosphinic acid ethyl ester (trade name TPO-L), 2- dimethylamino -2- benzyls -1- [4- (4- morpholinyls) benzene
Base] -1- butanone (trade name IHT-PI 910), 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone
At least one of (trade name 659), methyl benzoylformate (trade name MBF).
In some embodiments, the first organic solvent is acetone, ethyl acetate, tetrahydrofuran, N, N- dimethyl formyls
At least one of amine, dichloromethane, isopropanol, espeleton.
In some embodiments, the power of UV light is 100~1000W, and magnetic stirring speed is 100~1000r/min,
Reaction time is 0~5h.
In some embodiments, inorganic salts are at least one of sodium sulphate, magnesium sulfate, sodium chloride, potassium chloride.
In some embodiments, drier be preferably in calcium chloride, phosphorus pentoxide, calcium sulfate, magnesium sulfate at least
It is a kind of.
Wherein, chitosan graft vegetable oil acid copolymer preparation method is as follows：
Vegetable oil acid is reacted with acetic anhydride sealing and prepares vegetable oil acid anhydrides (as shown in formula (IV)), then by chitosan
(as shown in formula (III)) and IodineSodium Solution mix, and vegetable oil acid anhydrides and pyridine is added dropwise, is uniformly mixed, isothermal reaction
It impregnated, washing, be dehydrated with the second organic solvent afterwards, be finally placed in vacuum drying chamber and be dried, obtain chitosan graft plant
Object oleic acid copolymer.
The synthetic reaction formula of chitosan graft vegetable oil acid (CS-g-VO) copolymer is as follows：
Wherein, n, k=0 or 1,0 < m+s <, 4,12 < h+m+n+s+t < 16.
Wherein, the viscosity average molecular weigh of chitosan is 1.2 × 103~2.5 × 105, deacetylation >=90%；Chitosan and iodine
The mass ratio for changing sodium is 1:1~1:6, the molar ratio of vegetable oil acid anhydrides and chitosan is 1:1~5:1, pyridine and vegetable oil acid anhydrides
Molar ratio be 2:1~6:1.
In some embodiments, in the synthetic reaction of chitosan graft vegetable oil acid copolymer reaction temperature be 50 DEG C~
80 DEG C, the reaction time is 6~16h.
In some embodiments, the second organic solvent is at least one of acetone, ether, ethyl alcohol；Drying temperature is
40~80 DEG C, drying time is 4~48h.
The present invention is reacted for substrate material using mercaptan-alkene clicking chemistry so that vegetable oil acid-is chitosan-based, poly- by shell
Amino in sugar carries out ester exchange reaction with polyunsaturated vegetable oil acid fat；Then existed by the double bond on sulfydryl and vegetable oil long-chain
Click-reaction under ultraviolet light introduces long-chain, C-S keys, prepares the chitosan-based polyalcohol of vegetable oil acid-, can not only utilize shell
Plasticity, the antibiotic property of glycan, and the flexibility of polyunsaturated vegetable oil fat long-chain can be utilized, prepare multifunctional groups biomass
Polyalcohol.
Still another aspect according to the present invention provides the chitosan-based polyalcohol of above-mentioned vegetable oil acid-in UV photocuring materials
Application in terms of material, adhesive, ink and polyurethane material.
Description of the drawings
Fig. 1 is the infrared spectrum comparison diagram of the linoleic acid and the chitosan-based polyalcohol of linoleic acid-of an embodiment of the present invention,
Wherein a, b are respectively linoleic acid, the chitosan-based polyalcohol of linoleic acid-；
Fig. 2 is the nucleus magnetic hydrogen spectrum comparison diagram of the linoleic acid and the chitosan-based polyalcohol of linoleic acid-of an embodiment of the present invention,
Wherein a, b are respectively the chitosan-based polyalcohol of linoleic acid-, linoleic acid.
Specific implementation mode
The invention will now be described in further detail with reference to the accompanying drawings.
1 linoleic acid of embodiment-chitosan-based polyalcohol
The preparation method of the chitosan-based polyalcohol of linoleic acid-, is as follows
1) preparation of chitosan graft linoleic acid copolymer：
It weighs 29.85g linoleic acid and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath adds
125 DEG C of heat reacts 4h.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous linoleic acid
Acid anhydride liquid, it is dry, it is sealed spare.It is 1.0 × 10 to weigh viscosity average molecular weigh5, chitosan 1g that deacetylation is 93%, it is molten
Solution is added 70mL methanol and is vigorously stirred in 30mL glacial acetic acids 1% (v/v) aqueous solution, makes solution system in the uniform shape of clarification
Sodium iodide 2g is added in state, and linoleic acid acid anhydride and pyridine is added dropwise in mixing, and Linoleic acid acid anhydride/amino of chitosan reacts molar ratio
4:1, pyridine and linoleic acid anhydride reactant molar ratio 4:1, being vigorously stirred makes it be uniformly mixed；8h is reacted at 80 DEG C, is soaked with acetone
Bubble, washing 3 times, are washed 3 times after being dehydrated with ether with ethyl alcohol, for 24 hours in 60 DEG C of vacuum drying, obtain chitosan graft linoleic acid.
2) preparation of the chitosan-based polyalcohol of linoleic acid-：
By the chitosan graft linoleic acid copolymer and 2 mercapto ethanol, photoinitiator 2,4,6- trimethyls obtained by step 1)
Benzoyl-diphenyl phosphine oxide (TPO) is uniformly mixed, and is placed in the photochemical reaction instrument of 600W power, magnetic agitation
4h is reacted, the molar ratio of wherein 2 mercapto ethanol and chitosan graft linoleic acid copolymer is 3:1,2,4,6- trimethylbenzoyl
The amount of base-diphenyl phosphine oxide (TPO) is the 1.5% of system gross mass, mixing speed 500r/min.After reaction, it uses
Organic solvent ethyl acetate dilutes, and is washed 3~4 times through supersaturated metabisulfite solution, to remove unreacted 2 mercapto ethanol, then
It is dried by phosphorus pentoxide, filtering, removing organic solvent finally by Rotary Evaporators is placed in vacuum drying chamber
It is dry, obtain the chitosan-based polyalcohol of linoleic acid-.
2 ricinoleic acid of embodiment-chitosan-based polyalcohol
The preparation method of the chitosan-based polyalcohol of ricinoleic acid-, is as follows：
1) preparation of chitosan graft ricinoleic acid copolymer：
It weighs 29.85g ricinoleic acids and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath
3h is reacted in 130 DEG C of heating.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous castor-oil plant
Oil anhydride liquid, it is dry, it is sealed spare.It is 1.5 × 10 to weigh viscosity average molecular weigh5, deacetylation be 91% chitosan
1g is dissolved in 30mL glacial acetic acids 1% (v/v) aqueous solution, and 70mL methanol is added and is vigorously stirred, and keeps solution system equal in clarification
Even state, is added sodium iodide 2g, and castor oil acid anhydrides and pyridine is added dropwise, and wherein castor oil acid anhydrides/amino of chitosan is anti-in mixing
Answer molar ratio 4:1, pyridine and ricinoleic acid anhydride reactant molar ratio 4:1, being vigorously stirred makes it be uniformly mixed；It is reacted at 80 DEG C
8h is impregnated with ethyl alcohol, is washed 3 times, washed 3 times with ethyl alcohol after being dehydrated with ether, for 24 hours in 60 DEG C of vacuum drying, obtains chitosan
Grafted castor oil acid.
2) preparation of the chitosan-based polyalcohol of ricinoleic acid-：
By the chitosan graft ricinoleic acid copolymer and 3- sulfydryl -1- propyl alcohol, photoinitiator 1- hydroxyls obtained by step 1)
Cyclohexyl phenyl ketone (184) is uniformly mixed, and is placed in the photochemical reaction instrument of 600W power, and magnetic agitation reacts 4h,
Wherein 3- sulfydryls -1- propyl alcohol and the molar ratio of chitosan graft ricinoleic acid copolymer is 3:1, photoinitiator 1- hydroxy-cyclohexyls
The amount of phenyl ketone (184) is the 1.5% of system gross mass, mixing speed 500r/min.After reaction, solvent acetic acid is used
Ethyl ester dilutes, and is washed 3~4 times through supersaturated Adlerika, to remove unreacted 3- sulfydryls -1- propyl alcohol, using anhydrous
Calcium chloride is dried, filters, and removing organic solvent finally by Rotary Evaporators is placed in drying in vacuum drying chamber, obtains
The chitosan-based polyalcohol of ricinoleic acid-.
3 linolenic acid of embodiment-chitosan-based polyalcohol
The chitosan-based polyols preparation method of linolenic acid-, is as follows：
1) preparation of chitosan graft linolenic acid copolymer：
It weighs 29.85g linolenic acids and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath
5h is reacted in 120 DEG C of heating.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous flax
Oil anhydride liquid, it is dry, it is sealed spare.It is 1.0 × 10 to weigh viscosity average molecular weigh5, deacetylation be 93% chitosan
1g is dissolved in 30mL glacial acetic acids 1% (v/v) aqueous solution, and 70mL methanol is added and is vigorously stirred, and keeps solution system equal in clarification
Even state, is added sodium iodide 2g, and linseed oil acid anhydrides and pyridine is added dropwise, and wherein linseed oil acid anhydrides/amino of chitosan is anti-in mixing
Answer molar ratio 4:1, pyridine and linolenic acid anhydride reactant molar ratio 4:1, being vigorously stirred makes it be uniformly mixed；It is reacted at 80 DEG C
8h is washed 3 times after being dehydrated with ether with ethyl alcohol with acetone soak, washing 3 times, for 24 hours in 60 DEG C of vacuum drying, obtains chitosan
It is grafted linolenic acid.
2) preparation of the chitosan-based polyalcohol of linolenic acid-：
By the chitosan graft linolenic acid copolymer and 3- sulfydryl -1- propyl alcohol, photoinitiator 2- hydroxyls-obtained by step 1)
2- methyl-1s-phenylacetone (trade name 1173) is uniformly mixed, and is placed in the photochemical reaction instrument of 600W power, magnetic force
It is stirred to react 4h, wherein 3- sulfydryls -1- propyl alcohol and the molar ratio of chitosan graft linolenic acid copolymer is 3:1, photoinitiator
The amount of 2- hydroxy-2-methyl -1- phenylacetones (trade name 1173) is the 1.5% of system gross mass, mixing speed 500r/
min.After reaction, it is diluted with organic solvent n,N-Dimethylformamide, is washed 3~4 times through supersaturated metabisulfite solution, with
Unreacted 3- sulfydryls -1- propyl alcohol is removed, is dried using calcium sulfate, filtering, is had finally by Rotary Evaporators removing
Solvent is placed in drying in vacuum drying chamber, obtains the chitosan-based polyalcohol of linolenic acid-.
4 eleostearic acid of embodiment-chitosan-based polyalcohol
The preparation method of the chitosan-based polyalcohol of eleostearic acid-, is as follows：
1) preparation of chitosan graft tung oil acid copolymer：
It weighs 29.85g eleostearic acids and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath adds
139 DEG C of heat reacts 4h.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous eleostearic acid
Acid anhydride liquid, it is dry, it is sealed spare.It is 1.2 × 10 to weigh viscosity average molecular weigh5, chitosan 1g that deacetylation is 90%, it is molten
Solution is added 70mL methanol and is vigorously stirred in 30mL glacial acetic acids 1% (v/v) aqueous solution, makes solution system in the uniform shape of clarification
Sodium iodide 2g is added in state, and tung oil acid anhydride and pyridine is added dropwise in mixing, and wherein tung oil acid anhydride/amino of chitosan reacts molar ratio
3:1, pyridine and tung oil acid anhydride react molar ratio 3:1, being vigorously stirred makes it be uniformly mixed；10h is reacted at 70 DEG C, is soaked with acetone
Bubble, washing 3 times, are washed 3 times after being dehydrated with ether with ethyl alcohol, are dried in vacuo 48h in 50 DEG C, are obtained chitosan graft eleostearic acid.
2) preparation of the chitosan-based polyalcohol of eleostearic acid-：
By the chitosan graft tung oil acid copolymer and 2- sulfydryl -3- propyl alcohol, photoinitiator 2- hydroxyls -2- obtained by step 1)
Methyl-1-phenylacetone (1173) is uniformly mixed, and is placed in the photochemical reaction instrument of 500W power, magnetic agitation reaction
3h, wherein 2- sulfydryls -3- propyl alcohol and the molar ratio of chitosan graft tung oil acid copolymer are 3:1, photoinitiator 2- hydroxyls -2- first
The amount of base -1- phenylacetones (1173) is the 2% of system gross mass, mixing speed 600r/min.After reaction, solvent is used
Ethyl acetate dilutes, and is washed 3~4 times by saturated nacl aqueous solution, to remove unreacted 2- sulfydryls -3- propyl alcohol, using
Anhydrous calcium chloride is dried, filters, and removing organic solvent finally by Rotary Evaporators is placed in drying in vacuum drying chamber,
Obtain the chitosan-based polyalcohol of eleostearic acid-.
5 oleic acid of embodiment-chitosan-based polyalcohol
The preparation method of the chitosan-based polyalcohol of oleic acid-, is as follows：
1) preparation of chitosan graft oleic acid copolymer：
It weighs 29.85g oleic acid and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath heating
125 DEG C, react 4h.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous oil anhydride liquid
Body, it is dry, it is sealed spare.It is 3.0 × 10 to weigh viscosity average molecular weigh5, deacetylation be 91% chitosan 1g, be dissolved in
In 40mL glacial acetic acids 1% (v/v) aqueous solution, 80mL methanol is added and is vigorously stirred, makes solution system in clarification uniform state, add
Enter sodium iodide 2g, mix, oil anhydride and pyridine is added dropwise, wherein oil anhydride/amino of chitosan reacts molar ratio 4:1, pyridine
With oleic acid anhydride reactant molar ratio 4:1, being vigorously stirred makes it be uniformly mixed；8h is reacted at 80 DEG C, with acetone soak, is washed 3 times,
It is washed 3 times with ethyl alcohol after being dehydrated with ether, for 24 hours in 60 DEG C of vacuum drying, obtains chitosan graft oleic acid.
(2) preparation of the chitosan-based polyalcohol of oleic acid-：By the chitosan graft oleic acid copolymer and 2,3- obtained by step 1)
Dimercaprol dimercaptopropanol, the mixing of photoinitiator 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone (659) are equal
It is even, it is placed in the photochemical reaction instrument of 800W power, magnetic agitation reacts 3h, wherein 2,3- dimercaprol dimercaptopropanol and chitosan
The molar ratio for being grafted oleic acid copolymer is 4:1, photoinitiator 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1-
The amount of acetone (659) is the 1.0% of system gross mass, mixing speed 700r/min.After reaction, organic solvent-acetone is used
Dilution is washed 3~4 times by saturated potassium chloride solution, dry using magnesium sulfate to remove unreacted 2,3- dimercaprol dimercaptopropanol
Dry processing, filtering remove organic solvent finally by Rotary Evaporators and are placed in drying in vacuum drying chamber, obtain oleic acid-shell
Glycan polylol.
6 oleic acid of embodiment-chitosan-based polyalcohol
The preparation method of the chitosan-based polyalcohol of oleic acid-, is as follows：
1) preparation of chitosan graft oleic acid copolymer：
It weighs 29.85g oleic acid and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath heating
125 DEG C, react 4h.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous oil anhydride liquid
Body, it is dry, it is sealed spare.It is 3.0 × 10 to weigh viscosity average molecular weigh5, deacetylation be 91% chitosan 1g, be dissolved in
In 40mL glacial acetic acids 1% (v/v) aqueous solution, 80mL methanol is added and is vigorously stirred, makes solution system in clarification uniform state, add
Enter sodium iodide 2g, mix, oil anhydride and pyridine is added dropwise, wherein oil anhydride-amino of chitosan reacts molar ratio 4:1, pyridine
With oleic acid anhydride reactant molar ratio 4:1, being vigorously stirred makes it be uniformly mixed；8h is reacted at 80 DEG C, with acetone soak, is washed 3 times,
It is washed 3 times with ethyl alcohol after being dehydrated with ether, for 24 hours in 60 DEG C of vacuum drying, obtains chitosan graft oleic acid.
2) preparation of the chitosan-based polyalcohol of oleic acid-：By the chitosan graft oleic acid copolymer and 2,3- obtained by step 1)
Dimercaprol dimercaptopropanol, the mixing of photoinitiator 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone (659) are equal
It is even, it is placed in the photochemical reaction instrument of 800W power, magnetic agitation reacts 3h, wherein 2,3- dimercaprol dimercaptopropanol and chitosan
The molar ratio for being grafted oleic acid copolymer is 4:1, photoinitiator 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -1-
The amount of acetone (659) is the 1.0% of system gross mass, mixing speed 700r/min.After reaction, with organic solvent dichloro
Methane dilutes, and is washed 3~4 times by saturated potassium chloride solution, to remove unreacted 2,3- dimercaprol dimercaptopropanol, using sulfuric acid
Magnesium is dried, filters, and removing organic solvent finally by Rotary Evaporators is placed in drying in vacuum drying chamber, obtains oil
Acid-chitosan-based polyalcohol.
7 linolenic acid of embodiment-chitosan-based polyalcohol
The chitosan-based polyols preparation method of linolenic acid-, is as follows：
1) preparation of chitosan graft linolenic acid copolymer：
It weighs 29.85g linolenic acids and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath
5h is reacted in 120 DEG C of heating.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous flax
Oil anhydride liquid, it is dry, it is sealed spare.It is 1.0 × 10 to weigh viscosity average molecular weigh5, deacetylation be 93% chitosan
1g is dissolved in 30mL glacial acetic acids 1% (v/v) aqueous solution, and 70mL methanol is added and is vigorously stirred, and keeps solution system equal in clarification
Even state, is added sodium iodide 2g, and linseed oil acid anhydrides and pyridine is added dropwise, and wherein linseed oil acid anhydrides/amino of chitosan is anti-in mixing
Answer molar ratio 4:1, pyridine and linolenic acid anhydride reactant molar ratio 4:1, being vigorously stirred makes it be uniformly mixed；It is reacted at 80 DEG C
8h is washed 3 times after being dehydrated with ether with ethyl alcohol with acetone soak, washing 3 times, for 24 hours in 60 DEG C of vacuum drying, obtains chitosan
It is grafted linolenic acid.
2) preparation of the chitosan-based polyalcohol of linolenic acid-：
By the chitosan graft linolenic acid copolymer and 6- sulfydryl hex- 1- alcohol, photoinitiator 1- hydroxyls obtained by step 1)
Cyclohexyl phenyl ketone (184) is uniformly mixed, and is placed in the photochemical reaction instrument of 600W power, and magnetic agitation reacts 4h,
Wherein 6- sulfydryls hex- 1- alcohol and the molar ratio of chitosan graft linolenic acid copolymer is 3:1, photoinitiator 1- hydroxy-cyclohexyls
The amount of phenyl ketone (184) is the 1.5% of system gross mass, mixing speed 500r/min.After reaction, organic solvent is used
Espeleton dilutes, and is washed 3~4 times through supersaturated metabisulfite solution, to remove unreacted 6- sulfydryls hex- 1- alcohol, using
Calcium sulfate is dried, filters, and removing organic solvent finally by Rotary Evaporators is placed in drying in vacuum drying chamber, obtains
The chitosan-based polyalcohol of linolenic acid-.
8 linoleic acid of embodiment-chitosan-based polyalcohol
The preparation method of the chitosan-based polyalcohol of linoleic acid-, is as follows
1) preparation of chitosan graft linoleic acid copolymer：
It weighs 29.85g linoleic acid and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath adds
125 DEG C of heat reacts 4h.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous linoleic acid
Acid anhydride liquid, it is dry, it is sealed spare.It is 1.0 × 10 to weigh viscosity average molecular weigh5, chitosan 1g that deacetylation is 93%, it is molten
Solution is added 70mL methanol and is vigorously stirred in 30mL glacial acetic acids 1% (v/v) aqueous solution, makes solution system in the uniform shape of clarification
Sodium iodide 2g is added in state, and linoleic acid acid anhydride and pyridine is added dropwise in mixing, and Linoleic acid acid anhydride/amino of chitosan reacts molar ratio
4:1, pyridine and linoleic acid anhydride reactant molar ratio 4:1, being vigorously stirred makes it be uniformly mixed；8h is reacted at 80 DEG C, is soaked with acetone
Bubble, washing 3 times, are washed 3 times after being dehydrated with ether with ethyl alcohol, for 24 hours in 60 DEG C of vacuum drying, obtain chitosan graft linoleic acid.
2) preparation of the chitosan-based polyalcohol of linoleic acid-：
By the chitosan graft linoleic acid copolymer and 1- sulfydryl -2- propyl alcohol, photoinitiator 2,4,6- tri- obtained by step 1)
Methyl benzoyl phenyl-phosphonic acid ethyl ester (TPO-L) is uniformly mixed, and is placed in the photochemical reaction instrument of 600W power, magnetic force
It is stirred to react 4h, wherein 1- sulfydryls -2- propyl alcohol and the molar ratio of chitosan graft linoleic acid copolymer is 3:1,2,4,6- front three
The amount of base benzoylphenyl phosphinic acid ethyl ester (TPO-L) is the 1.5% of system gross mass, mixing speed 500r/min.Reaction
After, it is diluted, is washed 3~4 times through supersaturated metabisulfite solution, to remove unreacted 1- mercaptos with organic solvent ethyl acetate
Base -2- propyl alcohol is dried, filtering using phosphorus pentoxide, and removing organic solvent finally by Rotary Evaporators is placed in
It is dry in vacuum drying chamber, obtain the chitosan-based polyalcohol of linoleic acid-.
9 ricinoleic acid of embodiment-chitosan-based polyalcohol
The preparation method of the chitosan-based polyalcohol of ricinoleic acid-, is as follows：
1) preparation of chitosan graft ricinoleic acid copolymer：
It weighs 29.85g ricinoleic acids and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath
3h is reacted in 130 DEG C of heating.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous castor-oil plant
Oil anhydride liquid, it is dry, it is sealed spare.It is 1.5 × 10 to weigh viscosity average molecular weigh5, deacetylation be 91% chitosan
1g is dissolved in 30mL glacial acetic acids 1% (v/v) aqueous solution, and 70mL methanol is added and is vigorously stirred, and keeps solution system equal in clarification
Even state, is added sodium iodide 2g, and castor oil acid anhydrides and pyridine is added dropwise, and wherein castor oil acid anhydrides/amino of chitosan is anti-in mixing
Answer molar ratio 4:1, pyridine and ricinoleic acid anhydride reactant molar ratio 4:1, being vigorously stirred makes it be uniformly mixed；It is reacted at 80 DEG C
8h is impregnated with ethyl alcohol, is washed 3 times, washed 3 times with ethyl alcohol after being dehydrated with ether, for 24 hours in 60 DEG C of vacuum drying, obtains chitosan
Grafted castor oil acid.
2) preparation of the chitosan-based polyalcohol of ricinoleic acid-：
By chitosan graft ricinoleic acid copolymer and 11- sulfydryl -1- undecyl alcohols, the photoinitiator 2,4 obtained by step 1),
6- trimethylbenzoy-diphenies phosphine oxide (TPO) is uniformly mixed, and is placed in the photochemical reaction instrument of 600W power,
Magnetic agitation reacts 4h, and wherein 11- sulfydryls -1- undecyl alcohols and the molar ratio of chitosan graft ricinoleic acid copolymer is 3:1, light
Initiator 2,4, the amount of 6- trimethylbenzoy-diphenies phosphine oxide (TPO) are the 1.5% of system gross mass, mixing speed
For 500r/min.After reaction, it is diluted with solvent ethyl acetate, is washed 3~4 times through supersaturated Adlerika, to remove
Unreacted 11- sulfydryls -1- undecyl alcohols are dried, filtering using anhydrous calcium chloride, are removed finally by Rotary Evaporators
Organic solvent is placed in drying in vacuum drying chamber, obtains the chitosan-based polyalcohol of ricinoleic acid-.
10 linoleic acid of embodiment-chitosan-based polyalcohol
The preparation method of the chitosan-based polyalcohol of linoleic acid-, is as follows
1) preparation of chitosan graft linoleic acid copolymer：
It weighs 29.85g linoleic acid and is poured into flask, 20.4g acetic anhydrides are added into flask, seal reaction system, oil bath adds
125 DEG C of heat reacts 4h.(78 DEG C, 90KPa) of decompression removes the acetic acid generated and unreacted acetic anhydride, obtains rufous linoleic acid
Acid anhydride liquid, it is dry, it is sealed spare.It is 1.0 × 10 to weigh viscosity average molecular weigh5, chitosan 1g that deacetylation is 93%, it is molten
Solution is added 70mL methanol and is vigorously stirred in 30mL glacial acetic acids 1% (v/v) aqueous solution, makes solution system in the uniform shape of clarification
Sodium iodide 2g is added in state, and linoleic acid acid anhydride and pyridine is added dropwise in mixing, and Linoleic acid acid anhydride/amino of chitosan reacts molar ratio
4:1, pyridine and linoleic acid anhydride reactant molar ratio 4:1, being vigorously stirred makes it be uniformly mixed；8h is reacted at 80 DEG C, is soaked with acetone
Bubble, washing 3 times, are washed 3 times after being dehydrated with ether with ethyl alcohol, for 24 hours in 60 DEG C of vacuum drying, obtain chitosan graft linoleic acid.
2) preparation of the chitosan-based polyalcohol of linoleic acid-：
By the chitosan graft linoleic acid copolymer and 3- sulfydryl -2- butanol, photoinitiator 2,4,6- tri- obtained by step 1)
Methyl benzoyl-diphenyl phosphine oxide (TPO) is uniformly mixed, and is placed in the photochemical reaction instrument of 600W power, magnetic force
It is stirred to react 4h, wherein 3- sulfydryls -2- butanol and the molar ratio of chitosan graft linoleic acid copolymer is 3:1,2,4,6- front three
The amount of base benzoyl-diphenyl phosphine oxide (TPO) is the 1.5% of system gross mass, mixing speed 500r/min.Reaction knot
Shu Hou is washed 3~4 times, to remove unreacted 3- sulfydryls-with organic solvent isopropanol through supersaturated metabisulfite solution
2- butanol is dried, filtering using phosphorus pentoxide, and removing organic solvent finally by Rotary Evaporators is placed in vacuum
It is dry in drying box, obtain the chitosan-based polyalcohol of linoleic acid-.
Utilize Nicolet companies of U.S. AVATAR 360FT-IR types Fourier infrared spectrographs and Switzerland Bruker
600 nuclear magnetic resonance chemical analysers of Biospin AG companies Bruker AV carry out the product prepared by 1~embodiment of embodiment 5
Structural Identification, it is as a result as follows：
The characterization result of embodiment 1 is as depicted in figs. 1 and 2, wherein a indicates linoleic infrared spectrogram, b tables in Fig. 1
The infrared spectrogram for showing the chitosan-based polyalcohol of linoleic acid-, by Fig. 1 it is found that spectrogram a in the absorption peak of 3016cm-1 is big
The stretching vibration peak of unsaturated double-bond in soya-bean oil long-chain；And the stretching vibration peak in spectrogram b at 3016cm-1 disappears,
Occurs wide and strong absorption peak at 3405cm-1, this is the stretching vibration absworption peak of-OH, this shows the sub- oil of chitosan graft
Acid.
A, b are respectively the chitosan-based polyalcohol of linoleic acid-, linoleic hydrogen nuclear magnetic resonance spectrogram in Fig. 2, are changed in spectrogram b
The characteristic peak of displacement study δ=5.3-5.5ppm is the C=C double bonds in soybean oil long-chain, and the double bond feature in spectrogram a herein
Peak disappears, and occurs at chemical shift δ=2.5~2.7ppm, δ=2.7~2.8ppm and δ=3.7-3.8ppm in spectrogram a
New absorption peak, δ=2.5~2.7ppm belong to the hydrogen on the tertiary carbon being connect with mercaptan, δ=2.7~2.8ppm and δ=3.7-
3.8ppm is respectively two methylene on 2 mercapto ethanol, and the mercaptan in soybean oil double bond is as grafted on by click-reaction
The characteristic peak of two methylene in molecule.
2~10 acquired results characteristic peak of embodiment is same as Example 1, and details are not described herein again.
The above testing result may indicate that under conditions of UV light, can by click-reaction using photoinitiator as catalyst
To prepare the chitosan-based polyalcohol of linoleic acid-.
Above-described is only some embodiments of the present invention.For those of ordinary skill in the art, not
Under the premise of being detached from the invention design, various modifications and improvements can be made, these belong to the protection model of the present invention
It encloses.
Claims (9)
1. the chitosan-based polyalcohol of vegetable oil acid-, which is characterized in that shown in structural formula such as formula (I)：
Wherein, n, k=0 or 1,0 < m+s <, 4,12 < h+m+n+s+t < 16；
R is C1~C4 alkyl.
2. preparing the preparation side of the chitosan-based polyalcohol of vegetable oil acid-described in claim 1 with free radical photo-initiation catalysis
Method, which is characterized in that steps are as follows：
Chitosan graft vegetable oil acid copolymer is mixed with mercaptan, free radical photo-initiation, under the irradiation of UV light, reaction is simultaneously
It is stirred to get to the chitosan-based polyalcohol of vegetable oil acid-described in claim 1.
3. preparation method according to claim 2, which is characterized in that the vegetable oil acid is ricinoleic acid, eleostearic acid, Asia
At least one of sesame oil acid, linoleic acid, oleic acid.
4. preparation method according to claim 3, which is characterized in that the mercaptan is 2 mercapto ethanol, 3- sulfydryls -1- third
Alcohol, 2,3- dimercaprol dimercaptopropanol, 1- sulfydryl -2- propyl alcohol, 2- sulfydryl -3- propyl alcohol, 6- sulfydryl hex- 1- alcohol, 3- sulfydryl -2- butanol, 11-
At least one of sulfydryl -1- undecyl alcohols.
5. preparation method according to claim 4, which is characterized in that the free radical photo-initiation is 2- hydroxyl -2- first
Base -1- phenylacetones, 1- hydroxycyclohexyl phenyl ketones, 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1-
Acetone, 2,4,6- trimethylbenzoy-diphenies phosphine oxide, 2,4,6- trimethylbenzoyl phenyls phosphinic acid ethyl ester, 2- bis-
Methylamino -2- benzyls -1- [4- (4- morpholinyls) phenyl] -1- butanone, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) benzene
Base] -1- acetone, at least one of methyl benzoylformate.
6. preparation method according to claim 5, which is characterized in that the power of the UV light is 100~1000W, stirring
Using magnetic agitation, mixing speed is 100~1000r/min, and the reaction time is 0~5h.
7. preparation method according to claim 6, which is characterized in that the preparation side of chitosan graft vegetable oil acid copolymer
Method is as follows：Vegetable oil acid is reacted with acetic anhydride sealing and prepares vegetable oil acid anhydrides, then mixes chitosan and IodineSodium Solution,
Vegetable oil acid anhydrides and pyridine is added dropwise, is uniformly mixed, impregnated, washing, be dehydrated with the second organic solvent after isothermal reaction,
It is finally placed in vacuum drying chamber and is dried to get to chitosan graft vegetable oil acid copolymer.
8. according to claim 7 any one of them preparation method, which is characterized in that the viscosity average molecular weigh of the chitosan is
1.2×103~2.5 × 105, deacetylation >=90%；The mass ratio of chitosan and sodium iodide is 1:1~1:6, vegetable oil acid anhydrides
Molar ratio with chitosan is 1:1~5:1, the molar ratio of pyridine and vegetable oil acid anhydrides is 2:1~6:1.
9. according to claim 2~8 any one of them preparation method, which is characterized in that chitosan graft vegetable oil acid is copolymerized
Reaction temperature is 50 DEG C~80 DEG C in the synthetic reaction of object, and the reaction time is 6~16h.
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