CN105254793A - PH-sensitive rosin-based polymer and preparation method and application thereof - Google Patents
PH-sensitive rosin-based polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a pH-sensitive rosin-based polymer and a preparation method and application thereof. The pH-sensitive rosin-based polymer is called as a dehydroabietic acid hydroxybutyl vinyl ether ester-acrylic polymer. The preparation method of the pH-sensitive rosin-based polymer comprises the steps that dehydroabietic acid and hydroxybutyl vinyl ether serve as the raw materials, EDC and DMAP serve as catalysts, dichloromethane serves as reaction solvent, and dehydroabietic acid hydroxybutyl vinyl ether ester is synthesized at room temperature. The intermediate product can be used for fine chemical engineering such as cosmetics, agriculture, pharmaceutical aspect and surface active agents. The dehydroabietic acid hydroxybutyl vinyl ether ester contains double bonds which are copolymerized with hydrophilic acrylic acid, the amphipathic pH-sensitive polymer is synthesized, and the polymer can be used in the aspects of medicine carrying, control over release of drugs, separation of sensors and biomass, enzyme fixation, waste water treatment and the like.
Description
Technical field
The present invention relates to dehydroabietic acid hydroxy butyl vinyl ether ester and have the preparation method of the quick rosinyl polymkeric substance of pH, specifically the present invention is that one has quick rosinyl polymkeric substance of pH and its preparation method and application.
Background technology
A kind of natural product of rosin; containing carboxyl, ternary phenanthrene ring frame; the suitable synthesis material as biologically active derivatives, its multiple colophony based functional polymkeric substance is also applied to the every field such as coated material, foodstuff additive, chemical industry catalysis, environment protection, fractionation by adsorption and medicine.
Chinese patent CN201310051464.0, open (bulletin) day: 2013.05.01, application (patent right) people: Guilin University of Technology, discloses a kind of method utilizing carboxylated rosin-based polymer microspheres to remove methylene blue in waste.Carboxylated rosin-based polymer microspheres is obtained with rosin hydroxyethyl methylacrylate carboxylate, vinylbenzene, acrylic monomer, Vinylstyrene, initiator Diisopropyl azodicarboxylate and dispersion agent gelatin, added in the waste water solution containing methylene blue, stir concussion certain hour, the methylene blue in waste water can be removed.Described waste water solution Methylene Blue concentration is 20 ~ 550 mg/litre, and when the pH value of waste water solution is 4 ~ 12, removal effect is best.The carboxylated rosin-based polymer microspheres that the method for this invention uses has the advantages such as composition is controlled, epigranular, green safety, eliminating rate of absorption are high, good biocompatibility.Present method is fast easy and simple to handle, is easy to large-scale promotion, expands the range of application of rosin simultaneously.Principal claim: a kind of method utilizing carboxylated rosin-based polymer microspheres to remove methylene blue in waste, it is characterized in that concrete steps are: the initiator Diisopropyl azodicarboxylate of 100 mass parts monomer mixtures and 0.1 ~ 2.0 mass parts adds in reaction vessel by the preparation of (1) carboxylated rosin-based polymer microspheres: a., after ultrasonic disperse is even, obtain oil phase, during dispersion, system temperature remains on 20 ± 1 DEG C; B. by the dispersion agent gelatin of 1 ~ 10 mass parts and the mixing of 100 ~ 800 mass parts deionized waters, and pass into nitrogen deoxygenation, be warming up to 80 DEG C and stir dispersion agent is dissolved completely, cool to 60 ± 1 DEG C afterwards, obtain aqueous phase; C. step (1) a being walked obtained oil phase joins in the obtained aqueous phase of step (1) b step, arranging stirring velocity is 500 ~ 800 revs/min, raised temperature reacts 3 ~ 6 hours under 70 ~ 85 DEG C of conditions, be warming up to 80 ~ 95 DEG C again, slaking terminates reaction after 1 ~ 2 hour, obtained intermediate product; D. the distilled water wash of intermediate product obtained for step (1) c step with 60 ± 1 DEG C is filtered with 350 order stainless (steel) wires for 10 ~ 15 times afterwards, vacuum-drying 12 hours at 60 DEG C, i.e. obtained flaxen carboxylated rosin-based polymer microspheres; In described monomer mixture, the mass ratio of rosin hydroxyethyl methylacrylate carboxylate, vinylbenzene, acrylic monomer and Vinylstyrene is 20:5 ~ 45:5 ~ 45:8 ~ 20, and acrylic monomer is methacrylic acid or vinylformic acid; (2) methylene blue in waste is removed: the carboxylated rosin-based polymer microspheres 1 mass parts step (1) d being walked preparation puts into the waste water solution containing methylene blue of 100 ~ 500 mass parts, with the rate oscillation of 150 revs/min absorption 3 ~ 360 minutes at 10 ~ 40 DEG C, leave standstill, namely filter carboxylated rosin-based polymer microspheres removes methylene blue in waste excessively; Described waste water solution Methylene Blue concentration is 20 ~ 550 mg/litre, and when the pH value of waste water solution is 4 ~ 12, removal effect is best.
Chinese patent: CN201010276104.7, open (bulletin) day: 2011.01.26, application (patent right) people: Guilin University of Technology, discloses a kind of method preparing rosin-based polymer microspheres.The method employing is nontoxic, raw material is sufficient, reproducible rosin is raw material, first carboxylate is obtained by reacting with β-hydroxyethyl methacrylate, again together with vinylbenzene as reaction monomers, Vinylstyrene is cross-linking monomer, gelatin is stablizer, adopt suspension polymerization to prepare micron order rosin-based polymer microspheres, thus obtained microsphere particle diameter is at 80-250 micron.This invention makes full use of China's rosin natural resource, and products therefrom can be used as pharmaceutical carrier, also can use as sorbent material and separating agent.Principal claim: a kind of method preparing rosin-based polymer microspheres, it is characterized in that concrete steps are: (1) obtains rosin and crylic acid hydroxy ester carboxylate, referred to as carboxylate with rosin, methacrylic acid-beta-hydroxy ethyl ester for the preparation method that raw material application number is the patent of invention of 200710085381.8; (2) in the reactor that condenser, thermometer, agitator are housed, add the stablizer gelatin that the deionized water of weight percent 70 ~ 80% and weight percent are 0.1-1%, about 60 DEG C are cooled to, as aqueous phase after being heated to 70 ~ 80 DEG C of dissolvings completely; (3) carboxylate step (1) obtained, with weight percent 4.6 ~ 8%, is mixed and made into monomer mixture with the vinylbenzene of weight percent 9.6 ~ 14.8%, the Vinylstyrene of weight percent 0.5 ~ 1%; Add the initiator Diisopropyl azodicarboxylate of weight percent 0.1 ~ 0.3% and the pore-creating agent toluene of weight percent 0 ~ 10% again, mix, as oil phase; (4) step (3) gained oil phase is added in step (2) gained aqueous phase, stir under 300-500r/min and be warming up to 80 DEG C of reactions after 3 hours, then being warming up to 90 DEG C of reactions end in 2 hours; By product distilled water wash after cooling, filter post-drying, obtain faint yellow rosin-based polymer microspheres, particle diameter is at 80-250 micron.
Being with carboxyl and having the polymer microballoon of adsorption function disclosed in above two files involved by two documents, does not all relate to the quick rosinyl polymer arts of PH.PH quick rosinyl polymkeric substance is a kind of simple linear polymer.The quick rosinyl polymkeric substance of pH can because of the difference of pH value, and produce the change of volume or form, this characteristic makes it have the function of medicine carrying.And human body intestines and stomach is divided into different pH regions, utilizes the difference of pH to change the mode regulating release, can positioning release medicine be realized, the separation of biomass, fixing of enzyme, sensor, sewage disposal etc.There is quick rosinyl polymerization of PH and preparation method thereof up to the present do not appear in the newspapers.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide the preparation method that a kind of dehydroabietic acid hydroxy butyl vinyl ether ester and acrylic acid copolymer synthesize the quick rosinyl polymkeric substance of pH.This polymkeric substance has pH responsiveness, can be used for medicine carrying and positioning release medicine, the separation of biomass, fixing of enzyme, sensor, sewage disposal etc.Provide wherein a kind of raw material simultaneously---the preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester.
Concrete scheme of the present invention is as follows:
One has the quick rosinyl polymkeric substance of pH,
(1) to be its chemical structural formula of dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer be the chemical name of this polymkeric substance:
(2) the quick rosinyl polymkeric substance of this pH has carboxyl :-COOH;
(3) the quick rosinyl polymkeric substance of this pH has rosinyl:
(4) n=5-100, m=55-160 in polymer formulae;
(5) physico-chemical property of the quick rosinyl polymkeric substance of this pH: outward appearance light yellow solid, is dissolved in dehydrated alcohol, trichloromethane, DMF, water etc.; Be insoluble in methylene dichloride, hexanaphthene, the organic solvents such as sherwood oil; Its number-average molecular weight is 6000-30000, and weight-average molecular weight is 20000-70000, and dispersion coefficient is 1.7-3.5, and fusing point is 50-150 DEG C.Number-average molecular weight refers to that the total mass of this polymerization system is average by molecule sum institute.Weight-average molecular weight be refer to the quality of this aggressiveness and molecular weight long-pending add and with the quality of aggressiveness add and ratio.
The above-described preparation method with the quick rosinyl polymkeric substance of pH, the method is with dehydroabietic acid hydroxy butyl vinyl ether ester, vinylformic acid for monomer, take AIBN as initiator, under 50-90 DEG C of condition, carry out radical polymerization, can obtain described there is the quick rosinyl polymkeric substance of pH.
The Raolical polymerizable principle described in preparation method of the quick rosinyl polymkeric substance of the above-described pH of having be AIBN at its temperature caused, produce 2-cyanopropyl free radical, activated monomer, makes its copolymerization.Equation is as follows:
Above-described AIBN chemistry azo-bis-isobutyl cyanide by name, molecular formula is C
8h
12n
4, structural formula is as follows:
The above-described preparation method with the quick rosinyl polymkeric substance of pH, described preparation method is: compare for 0.8-2:0.5-1.5 is dissolved completely in organic solvent by dehydroabietic acid hydroxy butyl vinyl ether ester and vinylformic acid with amount of substance, slowly be warming up to 50-90 DEG C, add the AIBN solution with corresponding organic solvent dissolution, lower the temperature after reaction 5-25h, obtain copolymer solution, dialysis removing small molecules, must have the quick rosinyl polymkeric substance of pH.
The above-described preparation method with the quick rosinyl polymkeric substance of pH, described organic solvent is trichloromethane, the combination of a kind of in tetrahydrofuran (THF), DMF, ethanol, hexanaphthene, methyl alcohol, ethyl acetate or any two kinds.
The above-described preparation method with the quick rosinyl polymkeric substance of pH, the solvent that described dialysis uses is dehydrated alcohol, any one in methyl alcohol, trichloromethane, hexanaphthene, ethyl acetate.
Arbitrary described preparation method with the quick rosinyl polymkeric substance of pH above, the amount adding initiator A IBN is the 2-10% of total monomer weight.
The above-described preparation method with the quick rosinyl polymkeric substance of pH, the temperature of described polyreaction controls at 60-80 DEG C.
The above-described preparation method with the quick rosinyl polymkeric substance of pH, described polymerization reaction time is 10-15h.
The above-described preparation method with the quick rosinyl polymkeric substance of pH, the preparation method of described dehydroabietic acid hydroxy butyl vinyl ether ester is: with dehydroabietic acid and hydroxy butyl vinyl ether for raw material, EDC and DMAP is catalyzer, at room temperature synthesizes dehydroabietic acid hydroxy butyl vinyl ether ester.
The above-described preparation method with the quick rosinyl polymkeric substance of pH, the concrete preparation method of described dehydroabietic acid hydroxy butyl vinyl ether ester:
Dehydroabietic acid, 4-hydroxy butyl vinyl ether, DMAP are dissolved in organic solvent according to amount of substance than the ratio for 1-2:1-2:0.5-4, be placed in the container with whipping appts and water-bath function, be stirred to material to dissolve completely, then under oxygen barrier, cold condition, add amount of substance is 4-hydroxy butyl vinyl ether 1-2 EDC doubly, finish and rise to room temperature reaction 24-72 hour, the solution containing dehydroabietic acid hydroxy butyl vinyl ether ester can be obtained; Revolve and steam except desolventizing, organic solvent dissolution, removal of impurities, crossing chromatography column purity can reach 98%.
The above-described preparation method with the quick rosinyl polymkeric substance of pH, in the concrete preparation method of described dehydroabietic acid hydroxy butyl vinyl ether ester, the chemistry of DMAP used is called DMAP, and molecular formula is C
7h
10n
2, structural formula is
The above-described preparation method with the quick rosinyl polymkeric substance of pH, in the concrete preparation method of described dehydroabietic acid hydroxy butyl vinyl ether ester, the chemistry of EDC used is called 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, and molecular formula is C
8h
18clN
3, structural formula is
The above-described preparation method with the quick rosinyl polymkeric substance of pH, it is characterized in that: in the concrete preparation method of described dehydroabietic acid hydroxy butyl vinyl ether ester product prepare that used organic solvent is methylene dichloride, the combination of a kind of in trichloromethane, tetrahydrofuran (THF), hexanaphthene, sherwood oil and DMF or any two kinds; Dissolve thick product use organic solvent be sherwood oil, hexanaphthene, ethyl acetate any one.
The above-described application with the quick rosinyl polymkeric substance of pH, this polymkeric substance can be used for medicine carrying, controls the release of medicine, the process of the separation of sensor, biomass, the fixing of enzyme and sewage.
The beneficial effect that the present invention obtains:
1, the invention provides a kind of pH quick rosinyl polymkeric substance thing, this polymer name is dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer, this invention utilizes renewable resources rosin and vinylformic acid as Material synthesis dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer, in raw material, dehydroabietic acid hydroxy butyl vinyl ether ester has double bond, with hydrophilic acrylic acid copolymer, the PH quick rosinyl polymkeric substance of synthesis has amphipathic.
2. the raw materials cost selected of the method is lower, and the pH photosensitive polymerization thing prepared has rosinyl and ester group structure, and this structure makes it have biodegradability compared with similar products, environmental friendliness.
3, the present invention take AIBN as initiator, and temperature of reaction is lower, and solvent for use is easy to get, and use polymerization process simple and safe, condition is gentleer, easily purifies.
4, this polymkeric substance is with carboxyl, has response to hydrogen ion, has pH susceptibility, in addition with the phenanthrene ring structure of rosin, has biocompatibility, may be used for medicine carrying and controls release.Even can be used for separation and the pH sensor of medicine.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of dehydroabietic acid hydroxy butyl vinyl ether ester.
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram of dehydroabietic acid hydroxy butyl vinyl ether ester.
Fig. 3 is the nuclear-magnetism carbon spectrum spectrogram of dehydroabietic acid hydroxy butyl vinyl ether ester.
Fig. 4 is the nucleus magnetic hydrogen spectrum spectrogram with the quick rosinyl polymkeric substance of PH.
Fig. 5 is the structural representation with the quick rosinyl polymkeric substance of pH.
Embodiment
Here is the case study on implementation that preparation has the quick rosinyl polymkeric substance of pH, explains preparation method of the present invention and application thereof.
Embodiment 1:
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.01mol dehydroabietic acid, 0.012 hydroxy butyl vinyl ether, 0.015molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds the methylene dichloride of 15ml, start stirring, until solid all dissolves.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.012mol, rapid sealed reaction device.After 72h, reaction solution is transferred in single port flask, rotary distillation, except desolventizing, obtain solid mixture, petroleum ether dissolution, removal of impurities.The transformation efficiency recording dehydroabietic acid is about 94.7%, productive rate about 94.7%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=1:1.2:1.5:1.2)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, trichloromethane (15ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.01mol) and vinylformic acid (0.008mol) are added in there-necked flask, start and stir after monomer dissolves completely, after intensification, add the chloroform soln dissolving 0.09gAIBN, about 30min has added.Then, slowly heat up, control at 50 DEG C, lower the temperature after reaction 10h, obtain copolymer solution.With dehydrated alcohol dialysis, i.e. the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=1:0.8)
Embodiment 2:
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.01mol dehydroabietic acid, 0.01mol hydroxy butyl vinyl ether, 0.005molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds the trichloromethane of 15ml, start stirring, until solid all dissolves.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.01mol, rapid sealed reaction device.After 24h, transferred to by reaction solution in single port flask, rotary distillation, except desolventizing, obtain solid mixture, hexanaphthene dissolves removal of impurities, and the transformation efficiency recording dehydroabietic acid is about 76.3%, productive rate about 48%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=1:1:0.5:1)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, tetrahydrofuran (THF) (15ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.008mol), vinylformic acid (0.15mol) are added in there-necked flask, start and stir after monomer dissolves completely, add after intensification and dissolve 0.28gAIBN tetrahydrofuran solution, about 30min has added.Then, slowly heat up, control at 55 DEG C, lower the temperature after reaction 14h, obtain copolymer solution.Methyl alcohol is dialysed, and obtains the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=0.8:1.5)
Embodiment 3
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.01mol dehydroabietic acid, 0.02mol hydroxy butyl vinyl ether, 0.04molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds the tetrahydrofuran (THF) of 15ml, start stirring, until solid all dissolves.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.02mol, rapid sealed reaction device.After 30h, transferred to by reaction solution in single port flask, rotary distillation, except desolventizing, obtain solid mixture, acetic acid ethyl dissolution, removal of impurities, the transformation efficiency recording dehydroabietic acid is about 90%, productive rate about 88%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=1:2:4:2)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, DMF (10ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.02mol) and vinylformic acid (0.005mol) are added in there-necked flask, heat up, add the DMF solution dissolving 0.83gAIBN, control at 60 DEG C, lower the temperature after reaction 5h, obtain copolymer solution.With successively with dehydrated alcohol dialysis, obtain the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=2:0.5)
Embodiment 4
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.01mol dehydroabietic acid, 0.01mol hydroxy butyl vinyl ether, 0.02molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds the DMF of 15ml, start stirring, until solid all dissolves.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.02mol, rapid sealed reaction device.After 35h, transferred to by reaction solution in single port flask, rotary distillation, except desolventizing, obtain solid mixture, hexanaphthene dissolves, and removal of impurities, the transformation efficiency recording dehydroabietic acid is about 95%, productive rate about 70%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=1:1:2:2)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, ethanol (10ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.02mol) and vinylformic acid (0.015mol) are added in there-necked flask, heat up, add the ethanolic soln dissolving 0.18gAIBN, control at 65 DEG C, lower the temperature after reaction 5h, obtain copolymer solution.With successively with hexanaphthene dialysis, obtain the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=2:1.5)
Embodiment 5
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.02mol dehydroabietic acid, 0.01mol hydroxy butyl vinyl ether, 0.005molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds the sherwood oil of 30ml, start stirring.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.02mol, rapid sealed reaction device.After 40h, transferred to by reaction solution in single port flask, rotary distillation, except desolventizing, obtain solid mixture, hexanaphthene dissolves, and removal of impurities, the transformation efficiency recording dehydroabietic acid is about 95%, productive rate about 25%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=2:1:0.5:1)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, methyl alcohol (10ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.01mol) and vinylformic acid (0.005mol) are added in there-necked flask, heat up, add the ethanolic soln dissolving 0.75gAIBN, control at 70 DEG C, lower the temperature after reaction 15h, obtain copolymer solution.With methyl alcohol dialysis, obtain the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=1:0.5)
Embodiment 6
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.02mol dehydroabietic acid, 0.02mol hydroxy butyl vinyl ether, 0.005molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds the hexanaphthene of 15ml, start stirring, until solid all dissolves.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.02mol, rapid sealed reaction device.After 45h, transferred to by reaction solution in single port flask, rotary distillation, except desolventizing, obtain solid mixture, petroleum ether dissolution, removal of impurities, the transformation efficiency recording dehydroabietic acid is about 95%, productive rate about 80%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=1:1:0.5:1)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, hexanaphthene (10ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.016mol) and vinylformic acid (0.01mol) are added in there-necked flask, heat up, add the cyclohexane solution dissolving 0.35gAIBN, control at 75 DEG C, lower the temperature after reaction 5h, obtain copolymer solution.With successively with ethyl acetate dialysis, obtain the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=1.6:1)
Embodiment 7
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.01mol dehydroabietic acid, 0.01mol hydroxy butyl vinyl ether, 0.02molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds the hexanaphthene of 15ml, start stirring, until solid all dissolves.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.02mol, rapid sealed reaction device.After 50h, transferred to by reaction solution in single port flask, rotary distillation, except desolventizing, obtain solid mixture, hexanaphthene dissolves, and removal of impurities, the transformation efficiency recording dehydroabietic acid is about 88%, productive rate about 75%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=1:1:2:2)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, ethyl acetate (10ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.02mol) and vinylformic acid (0.015mol) are added in there-necked flask, heat up, add the ethyl acetate solution dissolving 0.27gAIBN, control at 80 DEG C, lower the temperature after reaction 5h, obtain copolymer solution.With successively with methyl alcohol dialysis, obtain the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=2:1.5)
Embodiment 8
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.01mol dehydroabietic acid, 0.01mol hydroxy butyl vinyl ether, 0.02molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds 8ml trichloromethane and 8ml methylene dichloride, start stirring, until solid all dissolves.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.02mol, rapid sealed reaction device.After 55h, transferred to by reaction solution in single port flask, rotary distillation, except desolventizing, obtain solid mixture, petroleum ether dissolution, removal of impurities, the transformation efficiency recording dehydroabietic acid is about 98%, productive rate about 70%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=1:1:2:2)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, hexanaphthene (10ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.02mol) and vinylformic acid (0.015mol) are added in there-necked flask, heat up, add the ethyl acetate solution dissolving 0.90gAIBN, control at 85 DEG C, lower the temperature after reaction 5h, obtain copolymer solution.With successively with hexanaphthene dialysis, obtain the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=2:1.5)
Embodiment 9
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.01mol dehydroabietic acid, 0.02mol hydroxy butyl vinyl ether, 0.01molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds 8ml trichloromethane and 8ml tetrahydrofuran (THF), start stirring, until solid all dissolves.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.015mol, rapid sealed reaction device.After 60h, transferred to by reaction solution in single port flask, rotary distillation, except desolventizing, obtain solid mixture, petroleum ether dissolution, removal of impurities, the transformation efficiency recording dehydroabietic acid is about 92%, productive rate about 80%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=1:2:2:1.5)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, trichloromethane (10ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.02mol) and vinylformic acid (0.015mol) are added in there-necked flask, heat up, add the ethanolic soln of 0.27gAIBN, control at 90 DEG C, lower the temperature after reaction 12h, obtain copolymer solution.With successively with hexanaphthene dialysis, obtain the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=2:1.5)
Embodiment 10
(1) preparation method of dehydroabietic acid hydroxy butyl vinyl ether ester, is characterized in that with dehydroabietic acid and hydroxy butyl vinyl ether for raw material reaction generates.In advance stirrer is put into there-necked flask, add 0.01mol dehydroabietic acid, 0.02mol hydroxy butyl vinyl ether, 0.018molDMAP add in there-necked flask, there-necked flask is placed in ice-water bath, adds 8ml methylene dichloride and 8ml tetrahydrofuran (THF), start stirring, until solid all dissolves.Pass into nitrogen 15min, at 10 DEG C, add the EDC of 0.015mol, rapid sealed reaction device.After 65h, transferred to by reaction solution in single port flask, rotary distillation, except desolventizing, obtain solid mixture, petroleum ether dissolution, removal of impurities, the transformation efficiency recording dehydroabietic acid is about 92%, productive rate about 80%.(the amount of substance ratio of main raw material is: dehydroabietic acid: hydroxy butyl vinyl ether: DMAP:EDC=1:2:1.8:1.5)
(2) the quick multipolymer preparation method of pH, heating jacket is arranged on being equipped with stirrer there-necked flask, tetrahydrofuran (THF) (10ml), dehydroabietic acid hydroxy butyl vinyl ether ester (0.008mol) and vinylformic acid (0.005mol) are added in there-necked flask, heat up, add and dissolve 0.21gAIBN ethanolic soln, control at 75-80 DEG C, lower the temperature after reaction 12h, obtain copolymer solution.With successively with hexanaphthene dialysis, obtain the quick rosinyl polymkeric substance of pH.(the amount of substance ratio of main raw material is: dehydroabietic acid hydroxy butyl vinyl ether ester: vinylformic acid=0.8:0.5)
Two, the physico-chemical property of compound, spectral data and structure are determined
Infrared spectrometer (NicoletIS10)
High performance liquid chromatography (Agilent1260-HPLC)
LC-MS (ShimadzuLCMS-2010A)
Nuclear magnetic resonance spectrometer (BrukerAvance (600/400) MHz)
Plant and instrument: with NicoletIS10 determination of infrared spectroscopy infrared spectra; Nuclear magnetic resonance spectrum BrukerAvance (600/400) MHz nuclear magnetic resonance spectrometer measures, and analyzes, thus determine the chemical structural formula of this compound through carrying out detection to the product of embodiment 1.
Fig. 1, the infrared spectrum of dehydroabietic acid hydroxy butyl vinyl ether ester, at 3114cm
?1produce be C=C ?C in H ?H stretching vibration absorption peak, and 1654cm
?1the vibration absorption peak of C=C, in addition, 970cm ?1 be alkene C ?H out-of-plane vibration absorption peak.2943cm
?1and 2869cm
?1be saturated C ?the vibration absorption peak of H, and at 1386cm
?1be saturated C ?the flexural vibration peak of H.At 1728cm
?1absorption peak be C=O stretching vibration absorption peak on ester bond, and at 1169cm
?1be C ?C (=O) ?the stretching vibration absorption peak of carbon-carbon single bond in 0.At 1603cm
?1, 1489cm
?1, 1466cm
?1the framework characteristic peak of phenyl ring, and at 816cm
-1it is the C-H out-of-plane deformation vibration absorption peak on phenyl ring.At 1249cm
-1it is the C-O stretching vibration absorption peak in O-C=C.Compared with the infrared spectrum of dehydroabietic acid, add 3114cm
-1c-H stretching vibration absorption peak in C=C-H and 1654cm
-1be the vibration absorption peak of C=C, and lacked carboxyl peak, it can thus be appreciated that the carboxyl esterification of dehydroabietic acid, has synthesized target product.
Fig. 2, the nucleus magnetic hydrogen spectrum figure of dehydroabietic acid hydroxy butyl vinyl ether ester, belonged to known by structural analysis, 7.26ppm place is deuterochloroform solvent peak, the position residing for three hydrogen on the fragmentation condition at three groups of peaks (two doublets, unimodal) of 6.88-7.19ppm and dehydroabietic acid hydroxy butyl vinyl ether ester phenyl ring coincide.The division situation of the quartet of 6.48-6.41ppm is corresponding with the hydrogen position of (i.e. No. 28 carbon) on the double key carbon that ehter bond is connected.And on the division peak that 3.96-4.19ppm occurs and the carbon that is connected with ester bond of coupling peak in the hydrogen position of (i.e. No. 23 carbon) and double bond the position of the hydrogen of carbon (i.e. No. 29 carbon) be consistent.In addition, the triple splitting peak of 3.70-3.68ppm is consistent with the hydrogen position of (i.e. No. 26 carbon) on the carbon that ehter bond is connected.And the integration at the division peak of hydrogen generates ester than illustrating that for 1:2:2:2 dehydroabietic acid and hydroxyl butyl vinyl ether react on corresponding carbon. in addition, the molecular weight recorded by LC-MS is 398 generations demonstrating dehydroabietic acid hydroxy butyl vinyl ether ester further.1HNMR(600MHz,CDCl3，δ，ppm)：δ7.17(d,J＝8.2Hz,1H-Ar),7.01(s,1H-Ar),6.89(s,1H-Ar),6.45(dd,J＝14.4,6.8Hz,1H-OCH＝),4.15(dd,J＝14.2,1.5Hz,1H-CH2＝),4.11(dd,J＝12.6,6.7Hz,2H-CH2＝),3.97(dd,J＝6.8,1.7Hz,1H-CH2＝),3.70(d,J＝5.5Hz,2H-CH2O),2.90–2.88(m,1H),2.86(d,J＝4.4Hz,1H),2.82(dd,J＝13.8,6.9Hz,1H),2.30(d,J＝12.3Hz,1H),2.25(dd,J＝12.4,1.6Hz,1H),1.83(tt,J＝16.0,9.8Hz,2H),1.76(d,J＝9.7Hz,2H),1.73–1.71(m,3H),1.64(d,J＝8.1Hz,1H),1.57(s,1H),1.50(t,J＝11.1Hz,1H),1.41(d,J＝12.4Hz,1H),1.27(s,3H),1.24–1.20(m,9H).
Fig. 3, the nuclear-magnetism carbon spectrum spectrogram of dehydroabietic acid hydroxy butyl vinyl ether ester, through measuring the signal of each carbon atom as described below: 13CNMR (100MHz, CDCl3, δ, ppm): 178.46 (20), 151.64 (28), 146.99 (10), 146.93 (12), 134.59 (9), 126.85 (11), 124.16 (13), 123.93 (14), 86.41 (29), 67.24 (26), 64.24 (23), 47.65 (4), 44.77 (3), 37.90 (6), 36.97 (2), 36.65 (5), 33.45 (15), 30.13 (8), 25.73 (24), 25.41 (25), 25.71 (24), 25.40 (25), 25.24 (19), 23.97 (16+17), 21.70 (18), 18.61 (7), 16.51 (1).
Fig. 4. the nucleus magnetic hydrogen spectrum spectrogram of dehydroabietic acid hydroxy butyl vinyl ether ester-acrylic acid copolymer polymkeric substance, belonged to known by structural analysis, 7.26ppm place is deuterochloroform solvent peak, the position residing for three hydrogen on the fragmentation condition at three groups of peaks (two doublets, unimodal) of 6.88-7.19ppm and dehydroabietic acid hydroxy butyl vinyl ether ester phenyl ring coincide.Quartet at 6.48-6.41ppm place disappears, and transfer to 3.56-3.62ppm (i.e. d carbon location), be coupled overlapping with the hydrogen on c carbon forms quartet, explanation double bond disappears, and at 6.50-6.60ppm also no signal peak, namely be the fignal center of the hydrogen do not occurred on acrylic double bond carbon, this two double bonds copolymerization is described.Also occur that the signal of free hydrogen (i.e. a hydrogen) is unimodal simultaneously and be in 4.91ppm, be consistent in the position of the fignal center of 4.01-4.16ppm with the hydrogen of the carbon on ester bond in addition, the copolymerization of dehydroabietic acid hydroxy butyl vinyl ether ester and vinylformic acid is described.1HNMR(600MHz,CD
3OD，δ，ppm)：δ7.12(s,1H-Ar),6.94(s,1H-Ar),6.84(s,1H-Ar),4.91(s,78H-COOH),4.10(s,2H-OCH
2),3.59(q,J＝7.1Hz,3H-CH2OCH)。
Further, random selecting embodiment 3, embodiment 4, embodiment 6, embodiment 8 and enforcement 9 preparation-obtained pH quick rosinyl polymkeric substance carry out identical detection with pH quick rosinyl polymkeric substance prepared by embodiment 1, all embodiments detect all corresponding with executing pH quick rosinyl polymkeric substance prepared by example 1 infrared spectrogram of the result that obtains, nucleus magnetic hydrogen spectrum figure, nuclear-magnetism carbon spectrogram are analysed figure and be identical, and describe prepared product circulation ratio fabulous.
This Compound nomenclature is by applicant further: dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer.
Three, further illustrate the purposes with the quick rosinyl polymkeric substance of pH with the following Examples, but protection domain is not limited only to following Application Example.Have the application of the quick rosinyl polymkeric substance of pH, this polymkeric substance can be used for medicine carrying, controls the release of medicine, the separation of sensor, biomass, the fixing of enzyme and sewage process.
Application Example 1
Weigh dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer (Mn=14062) 5mg and Whitfield's ointment 1mg that prepare, be dissolved in respectively in the phosphate buffer soln of pH=6.60 and pH=5.45, constant volume, be made into 100ml.The solution getting 5ml is respectively placed in the dialysis tubing that molecular weight cut-off is 8000D, after dialysis tubing rope is tied up, put into the phosphate buffer soln of corresponding 50ml, stir under the condition in greenhouse and carry out dynamic dialysis, get 0.5ml dialyzate at regular intervals, supplement the phosphate buffer soln of response simultaneously, obtaining sample adopts HPLC to measure, by more salicylic peak area, in the dialyzate of known pH=6.60, salicylic content is higher, and get to 50% in 24h burst size, and the Whitfield's ointment burst size of pH=5.54 gets to 36% at 24h, illustrate that dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer can medicine carrying thus, and be subject to the impact of pH, release can be controlled according to pH, pH sensor material can also be used as.
Application Example 2
Configuration ferric chloride Solution 5.21mg/ml, get 25ml in Erlenmeyer flask, weighing 20mg dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer (Mn=14062) throws in Erlenmeyer flask, and good seal Erlenmeyer flask, is placed in the horizontal constant temperature oscillator of 30 DEG C, and start timing, get supernatant 5ml every 8h to dilute for 20ml, be titration with the sodium hydroxide solution demarcated, its concentration is 1.23mg/ml, with phenolphthalein as indicator, record consumes the volume of sodium hydroxide each time.Deduct the amount of the iron(ic) chloride reacted with sodium hydroxide by the amount of initial iron ion, obtain the amount of the adsorbing chlorinated iron of dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer.About 30h gets to maximal absorptive capacity, known by calculating, and the amount of adsorbing each time increases successively, but adsorption rate is more and more slower, and finally reaching maximal absorptive capacity is 15.39mg/20mg.Illustrate that polymkeric substance has adsorption to iron metal ion thus, can iron metal ion in absorption effluent, can adsorb the iron metal ion smelting plant effuent, this polymkeric substance may be used for sewage disposal.
Application Example 3
Accurately take 20mg dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer (Mn=14062) in arid zones plug Erlenmeyer flask, then 25.00ml5.66mg/mL copper standardized solution and 25.00ml4.96mg/mL copper standardized solution is added respectively, be stoppered glass stopper separately, with plastic paper sealing (bungee ties), temperature is 30 DEG C, concussion absorption in THZ-82 water-bath constant temperature oscillator, after 8 hours, accurately 5ml solution is respectively got with transfer pipet, with the titration of EDTA standardized solution, murexide makes indicator, repeated to get every 8 hours later and once carry out titration, saturated extent of adsorption is reached to adsorptive capacity.In initial for some time, copper absorption speed is very fast, and the absorption of 24 hours resins reaches balance substantially.Dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer is to Cu
2+adsorptive capacity be 20.11mg/20mg.And the adsorptive capacity of nickel ion is less, maximal absorptive capacity can reach 3.53mg/ml.According to the difference of material and the difference of adsorptive capacity, different substances can be separated.
Application Example 4
Weighing 5g dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer is dissolved in the methylene dichloride of 30ml, under magnetic stirring, 10% protein enzyme solution of 10ml is dripped in this solution, sealing stirring is spent the night, suction filtration, washing, obtains the immobilized proteolytic enzyme 5.8g of dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer.Product Activity is 5.2mg.g
-1.5min
-1
Application Example 5
Weigh 5g dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer and be placed in Erlenmeyer flask, add the glucose solution of 25ml35mg/ml, be stoppered glass stopper, with plastic paper sealing (bungee ties), temperature is 30 DEG C, concussion absorption in THZ-82 water-bath constant temperature oscillator, after 27h, reach adsorption equilibrium, the change in concentration of glucose before and after absorption is measured with HPLC, known by detection computations, the maximal absorptive capacity of glucose can reach 108mg/5g. as can be seen here, dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer may be used for adsorbing glucose, can the separation of applying biological matter.
Claims (12)
1. there is the quick rosinyl polymkeric substance of pH, it is characterized in that:
(1) to be its chemical structural formula of dehydroabietic acid hydroxy butyl vinyl ether ester-acrylate copolymer be the chemical name of this polymkeric substance:
(2) the quick rosinyl polymkeric substance of this pH has carboxyl :-COOH;
(3) the quick rosinyl polymkeric substance of this pH has rosinyl:
(4) n=5-50, m=55-160 in polymer formulae;
(5) physico-chemical property of the quick rosinyl polymkeric substance of this pH: outward appearance light yellow solid, is dissolved in dehydrated alcohol, trichloromethane, DMF, water etc.; Be insoluble in methylene dichloride, hexanaphthene, the organic solvents such as sherwood oil; Its number-average molecular weight is 6000-30000, and weight-average molecular weight is 20000-70000, and dispersion coefficient is 1.7-3.5, and fusing point is 50-150 DEG C.
2. one kind has the preparation method of the quick rosinyl polymkeric substance of pH as claimed in claim 1, it is characterized in that: the method is for monomer with dehydroabietic acid hydroxy butyl vinyl ether ester, vinylformic acid, take AIBN as initiator, under 50-90 DEG C of condition, carry out radical polymerization, can obtain described there is the quick rosinyl polymkeric substance of pH.
3. the preparation method with the quick rosinyl polymkeric substance of pH according to claim 2, it is characterized in that: described preparation method is: dehydroabietic acid hydroxy butyl vinyl ether ester and vinylformic acid are compared for 0.8-2:0.5-1.5 is dissolved completely in organic solvent with amount of substance, slowly be warming up to 50-90 DEG C, add the AIBN solution with identical organic solvent dissolution, lower the temperature after reaction 5-25h, obtain copolymer solution, dialysis removing small molecules, must have the quick rosinyl polymkeric substance of pH.
4. the preparation method with the quick rosinyl polymkeric substance of pH according to claim 3, it is characterized in that: described organic solvent is trichloromethane, tetrahydrofuran (THF), DMF, ethanol, hexanaphthene, methyl alcohol, ethyl acetate, in a kind of or combination of any two kinds.
5. the preparation method with the quick rosinyl polymkeric substance of pH according to claim 3, is characterized in that: the solvent that described dialysis uses is dehydrated alcohol, any one in methyl alcohol, trichloromethane, hexanaphthene, ethyl acetate.
6., according to the arbitrary described preparation method with the quick rosinyl polymkeric substance of pH of claim 2-5, it is characterized in that: the amount adding initiator A IBN is the 2-10% of total monomer weight.
7. the preparation method with the quick rosinyl polymkeric substance of pH according to claim 6, is characterized in that: the temperature of described polyreaction controls at 60-80 DEG C.
8. the preparation method with the quick rosinyl polymkeric substance of pH according to claim 6, is characterized in that: described polymerization reaction time is 10-15h.
9. the preparation method with the quick rosinyl polymkeric substance of pH according to claim 2, it is characterized in that: the preparation method of described dehydroabietic acid hydroxy butyl vinyl ether ester is: with dehydroabietic acid and hydroxy butyl vinyl ether for raw material, EDC and DMAP is catalyzer, at room temperature synthesizes dehydroabietic acid hydroxy butyl vinyl ether ester.
10. the preparation method with the quick rosinyl polymkeric substance of pH according to claim 9, is characterized in that: the concrete preparation method of described dehydroabietic acid hydroxy butyl vinyl ether ester:
Dehydroabietic acid, 4-hydroxy butyl vinyl ether, DMAP are dissolved in organic solvent according to amount of substance than the ratio for 1-2:1-2:0.5-4, be placed in the container with whipping appts and water-bath function, be stirred to material to dissolve completely, then under oxygen barrier, cold condition, add amount of substance is 4-hydroxy butyl vinyl ether 1-2 EDC doubly, finish and rise to room temperature reaction 24-72 hour, the solution containing dehydroabietic acid hydroxy butyl vinyl ether ester can be obtained; Revolve and steam except desolventizing, organic solvent dissolution, removal of impurities, crossing chromatography column purity can reach 98%.
11. preparation methods with the quick rosinyl polymkeric substance of pH according to claim 9, it is characterized in that: in the concrete preparation method of described dehydroabietic acid hydroxy butyl vinyl ether ester thick product prepare that used organic solvent is methylene dichloride, the combination of a kind of in trichloromethane, tetrahydrofuran (THF), hexanaphthene, sherwood oil and DMF or any two kinds; The organic solvent that thick purifying products uses is sherwood oil, hexanaphthene, ethyl acetate any one.
12. application as claimed in claim 1 with the quick rosinyl polymkeric substance of pH, is characterized in that: this polymkeric substance can be used for medicine carrying, control the release of medicine, the process of the separation of sensor, biomass, the fixing of enzyme and sewage.
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| CN101215445A (en) * | 2007-12-28 | 2008-07-09 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives allyl ester |
| JP2009120543A (en) * | 2007-11-15 | 2009-06-04 | Milbon Co Ltd | Operation for correcting frizzy hair |
| CN101265392B (en) * | 2008-04-23 | 2010-04-21 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives methacrylic ester |
| CN103232349A (en) * | 2013-03-28 | 2013-08-07 | 中国林业科学研究院林产化学工业研究所 | Rosin or rosin derivative long chain flexible monomer preparation method |
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| JP2009120543A (en) * | 2007-11-15 | 2009-06-04 | Milbon Co Ltd | Operation for correcting frizzy hair |
| CN101215445A (en) * | 2007-12-28 | 2008-07-09 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives allyl ester |
| CN101265392B (en) * | 2008-04-23 | 2010-04-21 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives methacrylic ester |
| CN103232349A (en) * | 2013-03-28 | 2013-08-07 | 中国林业科学研究院林产化学工业研究所 | Rosin or rosin derivative long chain flexible monomer preparation method |
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