CN102746442A - Terpene-based macroporous adsorption resin and preparation method thereof - Google Patents
Terpene-based macroporous adsorption resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a terpene-based macroporous adsorption resin and a preparation method thereof. The name of the terpene-based macroporous resin is terpene maleate di(beta-acryloyloxyethyl)ester-methacrylic macroporous adsorption resin. The preparation method of the resin comprises the steps that: a natural perfume alpha-pinene is subjected to isomerization, and is subjected to diene addition with maleic anhydride, such that terpene maleic anhydride is obtained; the terpene maleic anhydride is subjected to an esterification reaction with ethylene glycol, such that terpene maleate di(beta-hydroxy ethyl)ester is prepared; the ester is subjected to an esterification reaction with acrylic acid, such that terpene maleate di(beta-acryloyloxyethyl)ester is obtained; the terpene maleate di(beta-acryloyloxyethyl)ester is adopted as a cross-linking agent, and is subjected to free radical suspension polymerization with a functional monomer methacrylic acid, such that the terpene maleate di(beta-acryloyloxyethyl)ester-methacrylic macroporous adsorption resin is prepared. The terpene-based macroporous adsorption resin is characterized by no toxicity, -COOH group, high specific surface area and large pore amount. The terpene-based macroporous adsorption resin can be used in extraction and separation of natural Chinese herbal medicines.
Description
Technical field
The present invention relates to a kind of macroporous adsorbent resin and preparation method thereof, more specifically is a kind of terpenyl macroporous adsorbent resin and preparation method thereof.
Background technology
At present; Method to the lixiviate of extraction common solvent, supercritical liq extraction or the recrystallization of herbal medicine such as vegeto-alkali, flavones, saponin(e Chinese herbal medicine effective ingredients; Weak point is that these method technical process are long, the not high or complex equipments of extraction yield, so chemist has been invented macroporous adsorbent resin and is used for the extraction separation herbal medicine; It is high and easy and simple to handle not only to separate Chinese herbal medicine effective ingredients, and the product purity of separating is high.Using the widest macroporous adsorbent resin at present is the polystyrene type polymer, and it is to be skeleton with the PS, adopts the macroporous adsorbent resin of method complex functionalityizatioies such as copolymerization, grafting.Many scholars have synthesized the macroporous adsorbent resin of many special constructions according to different application requiring, but its used poisonous monomer styrene and Vinylstyrene can be residual, thereby have limited its application aspect the Chinese herbal medicine extracting separation.
Summary of the invention
The present invention provides a kind of with the terpinene maleic anhydride that obtains with the maleic anhydride addition behind the natural perfume α-Pai Xi isomery for the deficiency that overcomes prior art; Through obtaining terpenes toxilic acid two (beta-hydroxy ethyl) ester with terepthaloyl moietie generation esterification; Obtain terpenes toxilic acid two (β-acryloxy ethyl) ester with vinylformic acid generation esterification again; Be linking agent with terpenes toxilic acid two (β-acryloxy ethyl) ester at last; Cause copolymerization with methylacrylic acid through radical and make terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin; This macroporous adsorbent resin has-COOH functional group, good mechanical stability and not have toxic substance residual; So it is more extensive than AB-8 purposes that terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin has, as be used to separate herbal medicine such as tetrahydropalmatine, berberine hydrochloride and flavonoid compound.
The present invention has two contents:
1. summary of the invention 1:
1) chemical name of crosslinking net kinetic energy based high polymer of the present invention is terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin; Structural formula:
2) physico-chemical property: appearance white spherical particle, acid number 30～100mgKOHg
-1, softening temperature is greater than 250 ℃, and degree of crosslinking is greater than 50%, and specific surface area is greater than 0.5m
2/ g, mean pore size is not dissolved in absolute ethyl alcohol, gasoline, hexanaphthene, toluene, acetone, acetate organic solvent greater than 20nm.
2. summary of the invention 2:
The preparation method of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin; Be to be linking agent with terpenes toxilic acid two (β-acryloxy ethyl) ester; Methylacrylic acid is a function monomer, and positive flow silane and butylacetate are for mixing pore-creating agent, and the azo class is an initiator; Adopt the suspension polymerization polymerization to obtain polymkeric substance; Remove the pore-creating agent in the polymkeric substance with the organic solvent wash-out, obtain terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin, concrete preparation method may further comprise the steps:
1) preparation of terpinene maleic anhydride
α-Pai Xi, ETHYLE ACETATE, phospho-molybdic acid and maleic anhydride are added in three mouthfuls of round-bottomed flasks, install TM, reflux condensing tube and whisking appliance, reflux 4h in 80 ℃ of water-baths; Be cooled to room temperature; Add hexanaphthene, be washed till neutrality with saturated sodium chloride aqueous solution, at pressure be then-the 0.1Mpa condition under rectifying; Collect 170～180 ℃ of cuts, obtain meeting the terpinene maleic anhydride of requirement of the present invention; Wherein: the ETHYLE ACETATE volume is 2 times of α-Pai Xi volume, and the phospho-molybdic acid quality is 1% of a α-Pai Xi quality, and the mol ratio of maleic anhydride and α-Pai Xi is 1: 1, and the hexanaphthene volume is the half the of α-Pai Xi volume.
2) preparation of terpenes toxilic acid two (beta-hydroxy ethyl) ester
In three mouthfuls of round-bottomed flasks, add terpinene maleic anhydride and terepthaloyl moietie, tosic acid and the band aqua hexanaphthene of step 1) preparation, load onto TM, water trap, whisking appliance and reflux condensing tube; Agitator, heating, temperature of reaction is controlled at 120～140 ℃; Reaction 2～7h, stopped reaction is cooled to room temperature; With deionized water repetitive scrubbing product, remove catalyzer and excessive terepthaloyl moietie, remove with the Rotary Evaporators evaporation then and anhydrate; Obtain terpenes toxilic acid two (beta-hydroxy ethyl) ester, surveying the product acid number should be less than 20mgKOHg
-1Wherein: the tosic acid quality is 1～8% of a terpinene maleic anhydride quality, and the mole of terpinene maleic anhydride and terepthaloyl moietie is 1: 2～1: 6, and the amount of hexanaphthene can control reaction temperature get final product.
3) preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester
In three mouthfuls of round-bottomed flasks, add step 2) terpenes toxilic acid two (beta-hydroxy ethyl) ester and Catalyzed by p-Toluenesulfonic Acid agent, vinylformic acid, Resorcinol stopper, octane solvent and the hexanaphthene band aqua of preparation, load onto TM, water trap, whisking appliance and reflux condensing tube; Agitator, heating, temperature of reaction is 90～100 ℃; Reaction 2～5h, stopped reaction is cooled to room temperature; Gradient method shifts out solvent, with deionized water repetitive scrubbing product, and the vinylformic acid of removing catalyzer, stopper and not reacted; Remove with the Rotary Evaporators evaporation then and anhydrate, obtain terpenes toxilic acid two (β-acryloxy ethyl) ester; Wherein: the tosic acid quality is 1～8% of terpenes toxilic acid two (beta-hydroxy ethyl) ester quality; Terpenes toxilic acid two (beta-hydroxy ethyl) ester and acrylic acid mol ratio are 1: 2～1: 5; The Resorcinol quality is 0.5～2.0% of a vinylformic acid quality; The octane volume is 2 times of terpenes toxilic acid two (beta-hydroxy ethyl) ester quality, and the amount of hexanaphthene can control reaction temperature get final product.
4) preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin
In three mouthfuls of round-bottomed flasks, add zero(ppm) water and sodium laurylsulfonate dispersion agent, load onto whisking appliance, water trap, reflux condensing tube and TM, under agitation condition, be heated to 45 ℃ and make it to form uniform aqueous phase.Wherein: sodium lauryl sulphate is 0.1 ‰～1 ‰ at the weight percent of aqueous phase;
In addition; Get terpenes toxilic acid two (β-acryloxy ethyl) ester and methylacrylic acid, butylacetate and positive flow silane mixing pore-creating agent that step 3) is prepared; Under the UW condition, it is dissolved fully; Add Diisopropyl azodicarboxylate (AIBN) initiator again, under the UW condition, make it to disperse to form uniform organic phase.Wherein: the mol ratio of terpenes toxilic acid two (β-acryloxy ethyl) ester and methylacrylic acid is 1: 1～1: 5; The volume ratio of butylacetate and positive flow silane is that 1: 1, total amount account for terpenes toxilic acid two (β-acryloxy ethyl) ester 50～150%, and Diisopropyl azodicarboxylate is 0.5～5% of terpenes toxilic acid two (β-acryloxy ethyl) ester and a methylacrylic acid total mass.
Under constant agitation speed, slowly add fully dissolved organic phase to water, pre-dispersed 5min slowly is warming up to 95 ℃ then in 1h, reaction 1h.
Finish after the reaction the product decompress filter; With 95 ℃ of distilled water flushings, drain; Sieve and get 20～60 orders, remove in snakelike fatty apparatus,Soxhlet's wash-out 24h with ethanol desolvate, pore-creating agent and low-molecular-weight polymkeric substance, washing; Drain, promptly getting product is terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin.
Above-mentioned synthetic terpenes toxilic acid two (β-acryloxy ethyl) ester linking agent structure does
The present invention has the following advantages:
1. the raw material α-Pai Xi is a natural perfume, and that ester-the methylacrylic acid macroporous adsorbent resin does not have toxic substance to synthetic terpenes toxilic acid two (β-acryloxy ethyl) is residual, can purify than the separation that AB-8 macroporous adsorbent resin more safely be used for herbal medicine.
2. the terpinene maleic anhydride molecule has the bridged ring structure, and skeleton is big, and the viscosity of synthetic terpenes toxilic acid two (β-acryloxy ethyl) ester is fit to the macroporous adsorbent resin of synthetic Kong Gengda.
3. raw material is easy to get, and is cheap, and application prospect is arranged.
Description of drawings
Fig. 1 is the infrared spectrogram of raw material terpinene maleic anhydride.
Fig. 2 is the ultraviolet spectrogram of raw material terpinene maleic anhydride.
Fig. 3 is the infrared spectrogram of intermediate product terpenes toxilic acid two (beta-hydroxy ethyl) ester.
Fig. 4 is the ultraviolet spectrogram of intermediate product terpenes toxilic acid two (beta-hydroxy ethyl) ester.
Fig. 5 is the MS figure of intermediate product terpenes toxilic acid two (beta-hydroxy ethyl) ester.
Fig. 6 is the infrared spectrogram of linking agent terpenes toxilic acid two (β-acryloxy ethyl) ester.
Fig. 7 is the ultraviolet spectrogram of linking agent terpenes toxilic acid two (β-acryloxy ethyl) ester.
Fig. 8 is the infrared spectrogram of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin.
Fig. 9 is that the desorption curve is inhaled-attached to terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin pore structure mensuration isothermal.
Figure 10 is that terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin pore structure is measured graph of pore diameter distribution.
Figure 11 is the photo of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin.
Figure 12 is terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin sem photograph.
Embodiment
One. preparing method's of the present invention technical scheme is following:
1. the first step α-Pai Xi is the synthetic terpinene maleic anhydride of raw material with maleic anhydride (or maleic anhydride) behind isomery under the effect of phospho-molybdic acid, and reaction equation is following:
2. second step terpinene maleic anhydride and the terepthaloyl moietie is that raw material passes through esterification and synthesized terpenes toxilic acid two (beta-hydroxy ethyl) ester, and reaction equation is following:
2.1 the selection of esterification reaction temperature
Along with the rising of temperature, the acid number of product descends gradually, and the acid number of product is more and more lower; Acid number is low more, explain with glycol reaction complete more because difficult the carrying out of reaction can not under very high reaction conditions, carry out, otherwise side reaction is serious, and acid number be too high, reaction not exclusively, so the acid number of product is less than 20mgKO Hg
-1, temperature of reaction is controlled at 120～140 ℃.
2.2 the selection of material ratio
Along with the terepthaloyl moietie ratio increases, the acid number of esterification products descends gradually, so the acid number of product is less than 20mgKO Hg
-1, terpinene maleic anhydride and terepthaloyl moietie mol ratio are 1: 2～1: 6.
2.3 the selection of catalyst levels
Adopt tosic acid to make terpinene maleic anhydride and terepthaloyl moietie esterification catalyst for reaction.Along with catalyst levels increases, the acid number of product descends gradually, surpasses a certain amount of back acid number and changes not quite, and present method selecting catalyst consumption is 1～8% to get final product.
2.4 the selection in reaction times
Along with the prolongation in reaction times, the acid number of product descends gradually, so the acid number of product is less than 20mgKOHg
-1, the reaction times is for should be 2～7h.
3. the 3rd step terpenes toxilic acid two (beta-hydroxy ethyl) esters and vinylformic acid reaction obtain terpenes toxilic acid two (β-acryloxy ethyl) ester
Esterification is reversible reaction; This experiment add with terpenes toxilic acid two (beta-hydroxy ethyl) ester mol ratio be that 1: 2～5 vinylformic acid promotes reaction forward to move; The tosic acid that adds terpenes toxilic acid two (beta-hydroxy ethyl) ester quality 1～8% is a catalyzer; Temperature of reaction is controlled at 90～100 ℃, reacting by heating 2～5h, in addition; Polymerization takes place in order to prevent vinylformic acid from high temperature reacting for a long time, needs to add the Resorcinol stopper of solvent cut and terpenes toxilic acid two (beta-hydroxy ethyl) ester quality 0.5～2.0%.
4. the 4th step was a linking agent with terpenes toxilic acid two (β-acryloxy ethyl) ester, made terpenes toxilic acid two of the present invention (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin with the function monomer methylacrylic acid through radical-initiated polymerisation.
4.1 the selection of polymeric reaction temperature
Along with polymeric reaction temperature improves, the polymkeric substance softening temperature raises, but the radical that produces in the too high reaction process of temperature is many, molecular weight and molecular weight, so present method polymeric reaction temperature is 60～100 ℃.
4.2 the selection of initiator Diisopropyl azodicarboxylate consumption
Along with initiator amount increases; The polymkeric substance softening temperature raises gradually; When being increased to when a certain amount of, the polymkeric substance softening temperature begins to descend, thus present method to select the amount of initiator be 0.5～5% of terpenes toxilic acid two (β-acryloxy ethyl) ester and methylacrylic acid total mass.
4.3 the selection of polymerization reaction time
Along with the prolongation in reaction times, the productive rate of product increases gradually, and when reaction reached 3h, the productive rate of product no longer changed, and it is 0.5～3h that preparation method of the present invention selects controlling reaction time.
Two. the affirmation of terpenes toxilic acid two of the present invention (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin
Definite method of product of the present invention comprises: acid number, softening temperature, degree of crosslinking and the solubleness in organic solvent of measuring the product of preparing by the inventive method; With the micropore determinator measure that the specific surface table is long-pending, aperture and distribution thereof; ESEM is measured its pattern, and with IR, GPC and MS the monomer and the product of the present invention of raw material, intermediate product, polymkeric substance is carried out monitoring analysis.
1. measure the acid number of linking agent with chemical analysis method (acid base titration), acid number should be less than 20mgKOHg
-1
2. utilize melting point detector to measure the softening temperature of product, softening temperature should be greater than 250 ℃.
3. measure the degree of crosslinking of product with the gel content method, degree of crosslinking should be greater than 50%.
4. should be greater than 0.5m with ASAP2020 type micropore determinator measurement the specific area
2/ g, mean pore size should be greater than 20nm.
5. with IR and ultraviolet-visible pectrophotometer raw material terpinene maleic anhydride of the present invention, intermediate product terpenes toxilic acid two (beta-hydroxy ethyl) ester, linking agent terpenes toxilic acid two (β-acryloxy ethyl) ester and final product terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin are carried out assay determination; Obtain their infrared spectrogram and ultraviolet spectrogram respectively, middle product terpenes toxilic acid two (beta-hydroxy ethyl) ester is analyzed with MS.Fig. 1 is the infrared spectrogram of raw material terpinene maleic anhydride; Fig. 2 is the ultraviolet spectrogram of raw material terpinene maleic anhydride; Fig. 3 is the infrared spectrogram of intermediate product terpenes toxilic acid two (beta-hydroxy ethyl) ester; Fig. 4 is the ultraviolet spectrogram of intermediate product terpenes toxilic acid two (beta-hydroxy ethyl) ester; Fig. 5 is the MS figure of intermediate product terpenes toxilic acid two (beta-hydroxy ethyl) ester; Fig. 6 is the infrared spectrum of linking agent terpenes toxilic acid two (β-acryloxy ethyl) ester; Fig. 7 is the ultraviolet spectrogram of linking agent terpenes toxilic acid two (β-acryloxy ethyl) ester; Fig. 8 is the infrared spectrum of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin, and Fig. 9 is that the desorption curve is inhaled-attached to terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin pore structure mensuration isothermal, and Figure 10 is that terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin pore structure is measured graph of pore diameter distribution; Figure 11 is the photo of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin, and Figure 12 is terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin sem photograph.The product that meets above condition is exactly terpenes toxilic acid two of the present invention (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin; And serve as according to detecting the specification of quality whether monitoring raw material, intermediate product, monomer and invention product meet terpenes toxilic acid two of the present invention (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin with these.
Preparing method of the present invention is with the starting material title specification place of production, and is as follows
Preparing method of the present invention is as follows with instrument, equipment, title, model, the place of production
Below in conjunction with embodiment the present invention is further described.
1. the preparation of terpinene maleic anhydride
The maleic anhydride of 100mL α-Pai Xi, 200mL ethyl acetate solvent, 0.84g phospho-molybdic acid and 60.5g in three mouthfuls of round-bottomed flasks of 500mL, is installed TM, reflux condensing tube and whisking appliance, 80 ℃ of water-bath 4h; Be cooled to room temperature, add the hexanaphthene of 50mL, be washed till neutral weak yellow liquid with saturated sodium chloride aqueous solution; Remove More Malay acid and catalyzer; 170～180 ℃ of cuts are collected in rectifying under-0.1Mpa reduced pressure then, obtain the 46.5g terpinene maleic anhydride.
2. the preparation of terpenes toxilic acid two (beta-hydroxy ethyl) ester
Get 20g by the terpinene maleic anhydride that step 1 prepares, place three mouthfuls of round-bottomed flasks of 250mL, add 1.6g Catalyzed by p-Toluenesulfonic Acid agent and 15mL terepthaloyl moietie; Load onto TM, water trap, whisking appliance and reflux condensing tube, agitator, heating; Temperature of reaction is controlled at 120～140 ℃, reaction 4h, stopped reaction; Be cooled to room temperature,, remove catalyzer and the terepthaloyl moietie that has not reacted with deionized water repetitive scrubbing product; Remove with the Rotary Evaporators evaporation then and anhydrate, surveying its acid number of product is 15.3mgKOHg
-1
3. the preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester
Get terpenes toxilic acid two (beta-hydroxy ethyl) ester that 10g prepares by step 2 in three mouthfuls of round-bottomed flasks of 250mL, adding the 0.8g tosic acid is catalyzer, 7mL vinylformic acid, 0.15g Resorcinol and 20mL octane, loads onto TM, water trap, whisking appliance and reflux condensing tube; Agitator, heating, temperature of reaction is controlled at 90～100 ℃; Reacting by heating 3.5h, stopped reaction is cooled to room temperature; Gradient method shifts out solvent, with deionized water repetitive scrubbing product, and the vinylformic acid of removing catalyzer, stopper and not reacted; Remove with the Rotary Evaporators evaporation then and anhydrate, product is subsequent use;
4. the preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin
In three mouthfuls of round-bottomed flasks of 500mL, add 200mL zero(ppm) water and 0.05g sodium laurylsulfonate dispersion agent, load onto whisking appliance, water trap, reflux condensing tube and TM, under the 250rpm stirring velocity, be heated to 45 ℃ and make it to form uniform aqueous phase.
In addition; Get terpenes toxilic acid two (β-acryloxy ethyl) ester that 6.4g is prepared by step 3; 3.8mL methylacrylic acid, 2.5mL butylacetate and 2.5mL positive flow silane are for mixing pore-creating agent, and UW dissolves it fully; Add 0.2550g Diisopropyl azodicarboxylate (AIBN) initiator again, UW makes it to disperse to form uniform organic phase.
Stirring velocity is constant slowly to add fully dissolved organic phase to water down, and pre-dispersed 5min slowly is warming up to 95 ℃ then in 1h, reaction 1h.
After reaction finishes with the product suction filtration; With 95 ℃ of distilled water flushings, drain, sieve and get 20～60 orders, remove in snakelike fatty apparatus,Soxhlet's wash-out 24h with ethanol desolvate, pore-creating agent and low-molecular-weight polymkeric substance; Washing; Drain, promptly getting product is terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin, acid number 32mgKOHg
-1, 292 ℃ of softening temperatures, degree of crosslinking 85%.
Embodiment 2
1. the preparation of terpinene maleic anhydride
According to step 1 preparation terpinene maleic anhydride among the embodiment 1.
2. the preparation of terpenes toxilic acid two (beta-hydroxy ethyl) ester
Get 50g by the terpinene maleic anhydride that step 1 prepares, place three mouthfuls of round-bottomed flasks of 500mL, add 1.5g Catalyzed by p-Toluenesulfonic Acid agent and 47.5mL terepthaloyl moietie; Load onto TM, water trap, whisking appliance and reflux condensing tube, agitator, heating; Temperature of reaction is controlled at 120～140 ℃, reacting by heating 4h, stopped reaction; Be cooled to room temperature,, remove catalyzer and the terepthaloyl moietie that has not reacted with deionized water repetitive scrubbing product; Remove with the Rotary Evaporators evaporation then and anhydrate, surveying its acid number of product is 13.7mgKOHg
-1
3. the preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester
Get terpenes toxilic acid two (beta-hydroxy ethyl) ester that 40g prepares by step 2 in three mouthfuls of round-bottomed flasks of 250mL, adding the 1.2g tosic acid is catalyzer, 28mL vinylformic acid, 0.3g Resorcinol and 80mL octane, loads onto TM, water trap, whisking appliance and reflux condensing tube; Agitator, heating, temperature of reaction is controlled at 90～100 ℃; Reacting by heating 3.5h, stopped reaction is cooled to room temperature; Gradient method shifts out solvent, with deionized water repetitive scrubbing product, and the vinylformic acid of removing catalyzer, stopper and not reacted; Remove with the Rotary Evaporators evaporation then and anhydrate, product is subsequent use;
4. the preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin
In three mouthfuls of round-bottomed flasks of 500mL, add 200mL zero(ppm) water and 0.05g sodium laurylsulfonate dispersion agent, load onto whisking appliance, water trap, reflux condensing tube and TM, under the 250rpm stirring velocity, be heated to 45 ℃ and make it to form uniform aqueous phase.
In addition; Get terpenes toxilic acid two (β-acryloxy ethyl) ester that 12.8g step 3 is prepared; 6.4mL methylacrylic acid, 5mL butylacetate and 5mL positive flow silane are for mixing pore-creating agent, and UW dissolves it fully; Add 1.0g Diisopropyl azodicarboxylate (AIBN) initiator again, UW makes it to disperse to form uniform organic phase.
Stirring velocity is constant slowly to add fully dissolved organic phase to water down, and pre-dispersed 5min slowly is warming up to 95 ℃ then in 1h, reaction 1h.
After reaction finishes with the product decompress filter; With 95 ℃ of distilled water flushings, drain, sieve and get 20～60 orders, remove in snakelike fatty apparatus,Soxhlet's wash-out 24h with ethanol desolvate, pore-creating agent and low-molecular-weight polymkeric substance; Washing; Drain, promptly getting product is terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin, acid number 35mgKOHg
-1, 295 ℃ of softening temperatures, degree of crosslinking 83%.
Embodiment 3
1. the preparation of terpinene maleic anhydride
According to step 1 preparation terpinene maleic anhydride among the embodiment 1.
2. the preparation of terpenes toxilic acid two (beta-hydroxy ethyl) ester
Get 100g by the terpinene maleic anhydride that step 1 prepares, place three mouthfuls of round-bottomed flasks of 500mL, add 6g Catalyzed by p-Toluenesulfonic Acid agent and 95mL terepthaloyl moietie; Load onto TM, water trap, whisking appliance and reflux condensing tube, agitator, heating; Temperature of reaction is controlled at 120～140 ℃, reacting by heating 4h, stopped reaction; Be cooled to room temperature,, remove catalyzer and the terepthaloyl moietie that has not reacted with deionized water repetitive scrubbing product; Remove with the Rotary Evaporators evaporation then and anhydrate, surveying its acid number of product is 14.2mgKOHg
-1
3. the preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester
Get terpenes toxilic acid two (beta-hydroxy ethyl) ester that 80g prepares by step 2 in three mouthfuls of round-bottomed flasks of 500mL, adding the 4.8g tosic acid is catalyzer, 56mL vinylformic acid, 0.9g Resorcinol and 160mL octane, loads onto TM, water trap, whisking appliance and reflux condensing tube; Agitator, heating, temperature of reaction is controlled at 90～100 ℃; Reacting by heating 3.5h, stopped reaction is cooled to room temperature; Gradient method shifts out solvent, with deionized water repetitive scrubbing product, and the vinylformic acid of removing catalyzer, stopper and not reacted; Remove with the Rotary Evaporators evaporation then and anhydrate, product is subsequent use;
4. the preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin
In three mouthfuls of round-bottomed flasks of 500mL, add 200mL zero(ppm) water and 0.05g sodium laurylsulfonate dispersion agent, load onto whisking appliance, water trap, reflux condensing tube and TM, under certain stirring velocity, be heated to 45 ℃ and make it to form uniform aqueous phase.
In addition; Get terpenes toxilic acid two (β-acryloxy ethyl) ester that 12.8g is prepared by step 3; 6.4mL methylacrylic acid, 7.5mL butylacetate and 7.5mL positive flow silane are pore-creating agent, and UW dissolves it fully; Add 0.51g Diisopropyl azodicarboxylate (AIBN) initiator again, UW makes it to disperse to form uniform organic phase.
Stirring velocity is constant slowly to add fully dissolved organic phase to water down, and pre-dispersed 5min slowly is warming up to 95 ℃ then in 1h, reaction 1h.
After reaction finishes with the product decompress filter; With 95 ℃ of distilled water flushings, drain, sieve and get 20～60 orders, remove in snakelike fatty apparatus,Soxhlet's wash-out 24h with ethanol desolvate, pore-creating agent and low-molecular-weight polymkeric substance; Washing; Drain, promptly getting product is terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin, acid number 38mgKOHg
-1, 298 ℃ of softening temperatures, degree of crosslinking 84%.
Embodiment 4
1. the preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester
Prepare terpenes toxilic acid two (β-acryloxy ethyl) ester according to embodiment 3 by step 3.
2. the preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin
In three mouthfuls of round-bottomed flasks of 500mL, add 200mL zero(ppm) water and 0.10g sodium laurylsulfonate dispersion agent, load onto whisking appliance, water trap, reflux condensing tube and TM, under certain stirring velocity, be heated to 45 ℃ and make it to form uniform aqueous phase.
In addition; Get terpenes toxilic acid two (β-acryloxy ethyl) ester that 12.8g is prepared by step 1; 6.4mL methylacrylic acid, 5mL butylacetate and 5mL positive flow silane are for mixing pore-creating agent, and UW dissolves it fully; Add 0.51g Diisopropyl azodicarboxylate (AIBN) initiator again, UW makes it to disperse to form uniform organic phase.
Stirring velocity is constant slowly to add fully dissolved organic phase to water down, and pre-dispersed 5min slowly is warming up to 95 ℃ then in 1h, reaction 1h.After reaction finishes with the product decompress filter; With 95 ℃ of distilled water flushings, drain, sieve and get 60～80 orders, remove in snakelike fatty apparatus,Soxhlet's wash-out 24h with ethanol desolvate, pore-creating agent and low-molecular-weight polymkeric substance; Washing; Drain, promptly getting product is terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin, specific surface area 3.15m
2/ g, pore volume 0.0179cm
3/ g, aperture 25.4nm.
Embodiment 5
1. precision takes by weighing tetrahydropalmatine reference substance 100mg (0.1007g), and the anhydrous alcohol solution with 50% places the 100ml volumetric flask, adds 50% absolute ethyl alcohol to scale, shakes up, and is subsequent use.
The accurate tetrahydropalmatine reference substance solution 0.5,1.0,1.5,2.0,2.5 of drawing, 3.0mL places the 50mL volumetric flask, and 50% absolute ethyl alcohol is diluted to scale, shakes up.As blank, measure different concns solution absorbency, drawing standard curve with zero(ppm) water in the 280nm place.The typical curve equation that obtains is:
Y＝14.647X+0.0045(1)
In the formula: Y is the absorbancy of tetrahydropalmatine, and X is the mass concentration (mg/mL) of tetrahydropalmatine, linearly dependent coefficient R
2=0.9997.
2. accurately take by weighing 20～40 purpose terpenes toxilic acids two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin (being accurate to 0.1mg) after the 0.3g pre-treatment; Add in the 100mL tool plug Erlenmeyer flask; Moving into 50mL concentration is the solution of 1.8mg/mL tetrahydropalmatine 50% absolute ethyl alcohol; In 30 ℃ of water bath with thermostatic control vibrators,, get supernatant liquid 1mL and be diluted to 50mL, measure its absorbancy with ultraviolet-visible pectrophotometer with the velocity fluctuation 4.5h of 150rpm.Try to achieve the equilibrium concentration of tetrahydropalmatine in the solution according to typical curve equation (1), by
Calculate the adsorptive capacity Q of tetrahydropalmatine
e
In the formula: Q
eBe adsorptive capacity (mg/g); V is liquor capacity (mL); C
oInitial concentration (mg/mL) for tetrahydropalmatine; C
eBe equilibrium concentration (mg/mL); W
oMacropore is inhaled the quality (g) of positive resin; X is the water cut (%) of macroporous adsorbent resin.
Experiment draws that terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid absorption with macroporous adsorbent resin tetrahydropalmatine adsorptive capacity is 139.3mg/g (dried resin).
Embodiment 6
1. accurately take by weighing berberine hydrochloride 10.90mg, be made into 50mL solution with distillation.Pipette absorption berberine hydrochloride solution 0.5mL, 1.0mL, 1.5mL, 2.0mL with liquid-transfering gun; 2.5mL 3.0mL places the 50mL volumetric flask respectively,, shakes up to scale marks with distilled water diluting; As reference, measure different concns solution absorbency, drawing standard curve with zero(ppm) water at the 345nm place.The typical curve equation of trying to achieve is:
Y＝25.242X+0.0051(R
2＝0.9997)(3)
In the formula: Y: be absorbancy;
X: be concentration.Try to achieve the equilibrium concentration of berberine hydrochloride in the solution by typical curve.
2. accurately taking by weighing the pretreated macroporous adsorbent resin of 0.3g (being accurate to 0.1mg) directly adds in the 100mL tool plug Erlenmeyer flask; Adding 50mL concentration is 2mg/mL berberine hydrochloride solution; In 30 ℃ of constant temperature oscillators with the velocity fluctuation 3.5h of 100rpm; Get supernatant liquid 1mL and be diluted to 100mL, measure the berberine hydrochloride solution absorbency with ultraviolet-visible pectrophotometer.Try to achieve the equilibrium concentration of berberine hydrochloride in the solution according to the typical curve equation, by formula
Try to achieve the adsorptive capacity Qe of macroporous adsorbent resin to berberine hydrochloride.
In the formula: Qe is the adsorptive capacity (mg/g) of macroporous adsorbent resin to solution; V is adsorbent solution volume (mL); C
0Initial concentration (mg/mL) for berberine hydrochloride solution before adsorbing; Ce is the equilibrium concentration (mg/mL) of absorption back berberine hydrochloride solution; W
0Be the quality (g) that takes by weighing the hygrometric state macroporous adsorbent resin; X is macroporous adsorbent resin water cut (%).
Experiment draws that terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid absorption with macroporous adsorbent resin berberine hydrochloride adsorptive capacity is 577.9mg/g (dried resin).
Claims (3)
1. terpenyl macroporous adsorbent resin is characterized in that:
1) chemical name of this terpenyl macroporous adsorbent resin is terpenes toxilic acid two (β-acryloxy ethyl)
Ester-methylacrylic acid macroporous adsorbent resin;
The structural formula of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin is following:
2) physico-chemical property: appearance white spherical particle, acid number 30～100mgKOHg
-1, softening temperature is greater than 250 ℃, and degree of crosslinking is greater than 50%, and specific surface area is greater than 0.5m
2/ g, mean pore size is not dissolved in absolute ethyl alcohol, gasoline, hexanaphthene, toluene, acetone and acetate organic solvent greater than 20nm.
2. the preparation method of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin; It is characterized in that, be to be linking agent with terpenes toxilic acid two (β-acryloxy ethyl) ester, and methylacrylic acid is a function monomer; Positive flow silane and butylacetate are for mixing pore-creating agent; The azo class is an initiator, adopts the suspension polymerization polymerization to obtain polymkeric substance, removes the pore-creating agent in the polymkeric substance with the organic solvent wash-out; Obtain terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin, concrete preparation method may further comprise the steps:
1) preparation of terpinene maleic anhydride
α-Pai Xi, ETHYLE ACETATE, phospho-molybdic acid and maleic anhydride are added in three mouthfuls of round-bottomed flasks, install TM, reflux condensing tube and whisking appliance, reflux 4h in 80 ℃ of water-baths; Be cooled to room temperature; Add hexanaphthene, be washed till neutrality with saturated sodium chloride aqueous solution, at pressure be then-the 0.1Mpa condition under rectifying; Collect 170～180 ℃ of cuts, obtain meeting the terpinene maleic anhydride of requirement of the present invention; Wherein: the ETHYLE ACETATE volume is 2 times of α-Pai Xi volume, and the phospho-molybdic acid quality is 1% of a α-Pai Xi quality, and the mol ratio of maleic anhydride and α-Pai Xi is 1: 1, and the hexanaphthene volume is the half the of α-Pai Xi volume;
2) preparation of terpenes toxilic acid two (beta-hydroxy ethyl) ester
In three mouthfuls of round-bottomed flasks, add terpinene maleic anhydride and terepthaloyl moietie, tosic acid and the band aqua hexanaphthene of step 1) preparation, load onto TM, water trap, whisking appliance and reflux condensing tube; Agitator, heating, temperature of reaction is controlled at 120～140 ℃; Reaction 2～7h, stopped reaction is cooled to room temperature; With deionized water repetitive scrubbing product, remove catalyzer and excessive terepthaloyl moietie, remove with the Rotary Evaporators evaporation then and anhydrate; Obtain terpenes toxilic acid two (beta-hydroxy ethyl) ester, surveying the product acid number should be less than 20mgKOHg
-1Wherein: the tosic acid quality is 1～8% of a terpinene maleic anhydride quality, and the mole of terpinene maleic anhydride and terepthaloyl moietie is 1: 2～1: 6, and the amount of hexanaphthene can control reaction temperature get final product;
3) preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester
In three mouthfuls of round-bottomed flasks, add step 2) terpenes toxilic acid two (beta-hydroxy ethyl) ester and vinylformic acid, tosic acid, Resorcinol stopper, solvent octane and the band aqua hexanaphthene of preparation, load onto TM, water trap, whisking appliance and reflux condensing tube; Agitator, heating, temperature of reaction is 90～100 ℃; Reaction 2～5h, stopped reaction is cooled to room temperature; Gradient method shifts out solvent, with deionized water repetitive scrubbing product, and the vinylformic acid of removing catalyzer, stopper and not reacted; Remove with the Rotary Evaporators evaporation then and anhydrate, obtain terpenes toxilic acid two (β-acryloxy ethyl) ester; Wherein: the tosic acid quality is 1～8% of terpenes toxilic acid two (beta-hydroxy ethyl) ester quality; Terpenes toxilic acid two (beta-hydroxy ethyl) ester and acrylic acid mol ratio are 1: 2～1: 5; The Resorcinol quality is 0.5～2.0% of a vinylformic acid quality; The octane volume is 2 times of terpenes toxilic acid two (beta-hydroxy ethyl) ester quality, and the amount of hexanaphthene can control reaction temperature get final product;
4) preparation of terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin
In three mouthfuls of round-bottomed flasks; Add zero(ppm) water and sodium laurylsulfonate dispersion agent; Load onto whisking appliance, water trap, reflux condensing tube and TM; Under agitation condition, be heated to 45 ℃ and make it to form uniform aqueous phase, wherein: sodium lauryl sulphate is 0.1 ‰～1 ‰ at the weight percent of aqueous phase;
In addition; Get terpenes toxilic acid two (β-acryloxy ethyl) ester and methylacrylic acid, butylacetate and positive flow silane mixing pore-creating agent that step 3) is prepared; Under the UW condition, it is dissolved fully; Add the Diisopropyl azodicarboxylate initiator again, under the UW condition, make it to disperse to form uniform organic phase; Wherein: the mol ratio of terpenes toxilic acid two (β-acryloxy ethyl) ester and methylacrylic acid is 1: 1～1: 5; The volume ratio of butylacetate and positive flow silane is that 1: 1, total amount account for terpenes toxilic acid two (β-acryloxy ethyl) ester 50～150%, and Diisopropyl azodicarboxylate is 0.5～5% of terpenes toxilic acid two (β-acryloxy ethyl) ester and a methylacrylic acid total mass;
Under constant agitation speed, slowly add fully dissolved organic phase to water, pre-dispersed 5min slowly is warming up to 95 ℃ then in 1h, reaction 1h;
Finish after the reaction the product decompress filter; With 95 ℃ of distilled water flushings, drain; Sieve and get 20～60 orders, remove in snakelike fatty apparatus,Soxhlet's wash-out 24h with ethanol desolvate, pore-creating agent and low-molecular-weight polymkeric substance, washing; Drain, promptly getting product is terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin.
3. a terpenes toxilic acid two (β-acryloxy ethyl) ester-methylacrylic acid macroporous adsorbent resin is characterized in that: (1) to (3) said step synthetic terpenes toxilic acid two (β-acryloxy ethyl) ester linking agent structure is
in the claim 2
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942450A (en) * | 2012-11-29 | 2013-02-27 | 中国林业科学研究院林产化学工业研究所 | 1-methyl-4-isopropyl-bicyclo[2,2,2]-2,3-dihydroxytoluene-5-octylene, as well as preparation method and application thereof |
| CN103265663A (en) * | 2013-05-30 | 2013-08-28 | 广西民族大学 | Glucosyl containing rosinyl macroporous resin and preparation method thereof |
| CN108640849A (en) * | 2018-05-03 | 2018-10-12 | 南京工业大学 | A kind of preparation method of ultraviolet light solidification terpenyl dendroid epoxy acrylate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59213783A (en) * | 1983-05-19 | 1984-12-03 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of pressure-sensitive hot-melt adhesive |
| CN101319036A (en) * | 2008-06-18 | 2008-12-10 | 广西民族大学 | Colophony based functional polymer and preparation method thereof |
| CN101555300A (en) * | 2009-05-19 | 2009-10-14 | 广西民族大学 | Method for preparing terpene resin |
| CN101768240A (en) * | 2010-01-26 | 2010-07-07 | 广西民族大学 | Abietyl-containing terpolymer and preparation method thereof |
-
2012
- 2012-05-15 CN CN201210150043.9A patent/CN102746442B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59213783A (en) * | 1983-05-19 | 1984-12-03 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of pressure-sensitive hot-melt adhesive |
| CN101319036A (en) * | 2008-06-18 | 2008-12-10 | 广西民族大学 | Colophony based functional polymer and preparation method thereof |
| CN101555300A (en) * | 2009-05-19 | 2009-10-14 | 广西民族大学 | Method for preparing terpene resin |
| CN101768240A (en) * | 2010-01-26 | 2010-07-07 | 广西民族大学 | Abietyl-containing terpolymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《广州化工》 20091231 朱华龙 等 beta-蒎烯与苯乙烯自由基共聚合的动力学 93、94、136页 1-3 第37卷, 第4期 * |
| 朱华龙 等: "β-蒎烯与苯乙烯自由基共聚合的动力学", 《广州化工》, vol. 37, no. 4, 31 December 2009 (2009-12-31) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942450A (en) * | 2012-11-29 | 2013-02-27 | 中国林业科学研究院林产化学工业研究所 | 1-methyl-4-isopropyl-bicyclo[2,2,2]-2,3-dihydroxytoluene-5-octylene, as well as preparation method and application thereof |
| CN103265663A (en) * | 2013-05-30 | 2013-08-28 | 广西民族大学 | Glucosyl containing rosinyl macroporous resin and preparation method thereof |
| CN103265663B (en) * | 2013-05-30 | 2015-04-22 | 广西民族大学 | Glucosyl containing rosinyl macroporous resin and preparation method thereof |
| CN108640849A (en) * | 2018-05-03 | 2018-10-12 | 南京工业大学 | A kind of preparation method of ultraviolet light solidification terpenyl dendroid epoxy acrylate |
| CN108640849B (en) * | 2018-05-03 | 2020-02-14 | 南京工业大学 | Preparation method of ultraviolet-curing terpene-based dendritic epoxy acrylate |
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Application publication date: 20121024 Assignee: GUANGXI DINGHONG RESIN CO.,LTD. Assignor: GUANGXI UNIVERSITY FOR NATIONALITIES Contract record no.: X2022450000425 Denomination of invention: Terpene based macroporous adsorption resin and its preparation method Granted publication date: 20140611 License type: Exclusive License Record date: 20221227 |
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