CN105585669A - Crosslinking agent, preparation method and application thereof, and CO2-responding polymer - Google Patents
Crosslinking agent, preparation method and application thereof, and CO2-responding polymer Download PDFInfo
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- CN105585669A CN105585669A CN201410591796.2A CN201410591796A CN105585669A CN 105585669 A CN105585669 A CN 105585669A CN 201410591796 A CN201410591796 A CN 201410591796A CN 105585669 A CN105585669 A CN 105585669A
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Abstract
The invention relates to the field of high-molecular chemistry and especially relates to a crosslinking agent, a preparation method and an application thereof, and a CO2-responding polymer formed by the crosslinking agent. The crosslinking agent is a compound represented as the structure formula (I) and has the two functional groups including a methacryloyl group and a diethylamine group at the same time, so that on one hand, the methacryloyl group, as a crosslinking chemical group which acts on a hydroxyl group in polyvinyl alcohol, can form a polymer with the polyvinyl alcohol as a frame in a crosslinking manner, and on the other end, the diethylamine group acts on CO2 to form a polymer which serves as the CO2-responding polymer.
Description
Technical field
The present invention relates to chemical field, particularly a kind of crosslinking agent, the preparation method of this crosslinking agentWith purposes, and a kind of photosynthesis-carbon dioxide response polymer being formed by this crosslinking agent.
Background technology
In recent years, can change (pH value, temperature, ionic strength, light, solvent by sensing external environmentDeng) and the intellectual material that changes in real time self performance parameter day by day receive people's concern. Along with to intellectual materialConstantly carrying out of research work, stimuli responsive type polymer has caused the more and more denseer interest of researcher,And become research object important in this advanced subject. Stimulating responsive refers to the physics due to external environmentThe variation of condition (as temperature and electromagnetic field) or electrochemical conditions (as pH and ionic strength) and cause that system is grandSee the larger change of character (as volume and permeability), be also referred to as intelligence or environmental sensitivity.
CO2Stimulating responsive polymer is the intelligent stimulus responsive polymers of a class that newly-developed gets up, and refers toPassing into and discharging CO2After, can there is the new polymers that invertibity changes in polymer property. Due to tuneIn control process, only relate to CO2And some inert gases and do not introduce other impurity, therefore there is many-sidePotential using value. CO2Stimulus responsive polymers refers to and is passing into and discharging CO2After, polymer propertyCan there is the new polymers that invertibity changes. Due to its unique mechanism of action and intelligentized transformation spyProperty, cause the extensive concern of academia. By CO2As the regulating switch of stimulus responsive polymers this without exceptionRead very attractive because only relate to CO in regulation process2Deng the passing into and discharge of inert gas, avoidThe generation of accessory substance and the pollution of system. A kind of like this stimuli responsive of " green " switch control that utilizes is poly-Compound will have potential application aspect sensor, surface-bonded agent and drug conveying carrier.
CO in prior art2The polymer of stimuli responsive is generally by CO2The polymer monomer polymerization of stimuli responsiveForm, wherein, CO2The polymer monomer of stimuli responsive comprises the styrene that contains amidino groups or amido functional groupClass and acrylic amide and acrylic ester compound, as follows:
CO2The polymer monomer of stimuli responsive is passing into and is discharging CO2After, its hydrophily and lipophile can be sent outRaw significant variation, and then affect hydrophily and the oil loving variation of polymer. In prior art, also do not haveAbout CO2The crosslinkable polymer monomer (crosslinking agent) of stimuli responsive and form polymer by crosslinking agentReport. CO2Stimuli responsive crosslinking agent will contribute to Novel carbon dioxide responsive polymer, as CO2StimulateConstructing of the intelligent polymer materials such as response resin and gel.
Given this, overcoming the existing defect of the prior art is the art problem demanding prompt solution.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of crosslinking agent, with by crosslinking agent and polyvinyl alcohol crosslinkedForm new photosynthesis-carbon dioxide response polymer.
The present invention adopts following technical scheme:
On the one hand, the invention provides a kind of crosslinking agent, for thering is the compound of structural formula (I),
The present invention also provides the preparation method of above-mentioned crosslinking agent, first, and at 45～60 DEG C, depositing of alkaliUnder, bromo-Isosorbide-5-Nitrae-bis-2,3-butanediol and excessive diethylamine are reacted and generate Isosorbide-5-Nitrae-bis-diethyl in polar solventAmido-2,3-butanediol; Then, at 8～12 DEG C, under the existence of triethylamine, by Isosorbide-5-Nitrae-bis-diethylamineBase-2,3-butanediol reacts generation in Carbon Dioxide dimethyl ester with methacrylic chloride.
In some embodiments, this preparation method comprises the steps:
At (1) 0 DEG C, in deionized water, alkali is dissolved, obtain aqueous slkali; Subsequently diethylamine is addedIn aqueous slkali, after 5～20 minutes, more bromo-Isosorbide-5-Nitrae-bis-2,3-butanediol is joined in aqueous slkali and mixed,To the first reactant liquor;
(2) the first reactant liquor is placed at 45～60 DEG C, reacts 7～12 hours, obtain containing Isosorbide-5-Nitrae-bis-or twoThe reactant liquor of ethylamino--2,3-butanediol;
(3) reactant liquor that contains Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol is carried out to reduced pressure concentration, gained is solidBody residue is dissolved in dimethyl carbonate, filters, and collects filtrate, then filtrate is carried out to reduced pressure concentration, obtainsIsosorbide-5-Nitrae-bis-diethylin-the 2,3-butanediol of purifying;
(4) in dimethyl carbonate, dissolve triethylamine and step (3) gained Isosorbide-5-Nitrae-bis-diethylin-2,3-Butanediol, obtains mixed liquor, after under nitrogen atmosphere, mixed liquor is cooled to 8～12 DEG C, then by methyl-propThe dimethyl carbonate lysate of alkene acyl chlorides is added in mixed liquor, stirring reaction 7～12 hours.
In some embodiments, also comprise the steps: afterwards in step (4)
(5) by step (4) gained solution filter, collect filtrate, after being removed to triethylamine, filtrate carries out oxygenChange aluminium column chromatography.
In some embodiments, described alkali be selected from NaOH, potassium hydroxide, calcium hydroxide, potassium tert-butoxide,TMAH, sodium hydride or hydrofining.
In some embodiments, the reaction temperature of step (2) is 50 DEG C. The reaction temperature of step (4) is10℃。
In some embodiments, alkali, diethylamine and the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-in step (1) moleThan being (1.5～3): (2～5): 1.
In some embodiments, alkali, diethylamine and the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-in step (1) moleThan being preferably 2.5:4:1.
The present invention provides above-mentioned crosslinking agent in the purposes of preparing in photosynthesis-carbon dioxide response polymer in addition.
On the other hand, the invention provides a kind of photosynthesis-carbon dioxide response polymer, wanted by polyvinyl alcohol and rightAsk the crosslinking agent reaction described in 1 to form.
In some embodiments, the preparation method of this polymer comprises the steps:
(1) in toluene, crosslinking agent and initator are dissolved, obtain organic liquor, wherein, described initatorFor azodiisobutyronitrile, the mol ratio of described crosslinking agent and described initator is 10:1;
(2) polyvinyl alcohol is dissolved in the water, obtains the aqueous solution;
(3) by after organic liquor and aqueous solution, under nitrogen atmosphere, gained mixed liquor is heated to 80 DEG C,React 4 hours.
Compared with prior art, beneficial effect of the present invention is: crosslinking agent of the present invention has methyl simultaneouslyTwo functional groups of acryloyl group and diethyl amido, on the one hand, the former is as doing with the hydroxyl of polyvinyl alcoholWith cross-linking chemistry group, crosslinkable forms the polymer taking polyvinyl alcohol as skeleton, on the other hand, the latterCan with CO2Effect, the polymer forming can be used as photosynthesis-carbon dioxide response polymer.
Brief description of the drawings
Fig. 1 is the synthesis path figure of a kind of crosslinking agent of providing of the embodiment of the present invention;
Fig. 2 is the preparation method's of a kind of crosslinking agent of providing of the embodiment of the present invention flow chart;
Fig. 3 is the Electronic Speculum figure of the photosynthesis-carbon dioxide response polymer prepared of the embodiment of the present invention 4;
Fig. 4 is the Electronic Speculum figure of the photosynthesis-carbon dioxide response polymer prepared of the embodiment of the present invention 4.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and realityExecute example, the present invention is further elaborated. Only should be appreciated that specific embodiment described hereinOnly, in order to explain the present invention, be not intended to limit the present invention.
In addition,, in each embodiment of described the present invention, involved technical characterictic needs only each otherBetween do not form conflict just can mutually combine.
The invention provides a kind of crosslinking agent, for thering is the compound of structural formula (I),
From structural formula (I), this crosslinking agent has methacryl and two function bases of diethyl amidoGroup, wherein, methacryl can be used as the cross-linking chemistry group with the hydroxyl effect of polyvinyl alcohol, crosslinkedForm taking polyvinyl alcohol for example as the polymer of skeleton, diethyl amido can with CO2Effect, what form is poly-Compound can be used as photosynthesis-carbon dioxide response polymer.
Fig. 1 shows a kind of synthesis path of crosslinking agent of the present invention, in the preparation side of crosslinking agent of the present inventionIn method, taking the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-as synthetic starting point, first, introduce diethyl amido, in 45～60 DEG CUnder, under the existence of alkali, bromo-Isosorbide-5-Nitrae-bis-2,3-butanediol and excessive diethylamine are reacted to raw in polar solventBecome Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol. Then, introduce methacryl, at 8～12 DEG C, threeUnder the existence of ethylamine, by Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol and methacrylic chloride at Carbon Dioxide diformazanIn ester, reaction generates crosslinking agent. Wherein, Et represents ethyl, that is :-C2H5。
Fig. 2 shows one of preparation method of the present invention preferably embodiment. Shown in Fig. 2,Preparation method mainly comprises four steps:
First, at 0 DEG C, in deionized water, alkali is dissolved, obtain aqueous slkali; Subsequently diethylamine is addedIn aqueous slkali, after 5～20 minutes, more bromo-Isosorbide-5-Nitrae-bis-2,3-butanediol is joined in aqueous slkali and mixed,To the first reactant liquor. Mentioned mixing in preparation method, can adopt conventional mixed method, as stirred,Make the bromo-2,3-butanediol uniform dissolution of Isosorbide-5-Nitrae-bis-. The present invention is to the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-and diethylamineSource does not have special restriction, adopts the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-well known to those skilled in the art and diethylAmine, as adopted commercial goods, also can adopt the Isosorbide-5-Nitrae-dibromo of preparing well known to those skilled in the artThe technical scheme of-2,3-butanediol and diethylamine is prepared voluntarily. In this step, in order to improve Isosorbide-5-Nitrae-dibromoThe conversion ratio of-2,3-butanediol, the diethylamine adding is excessive with respect to the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-. EnterOne step ground, the mol ratio of alkali, diethylamine and the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-in step is (1.5～3): (2～5): 1; Further, the mol ratio of alkali, diethylamine and the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-is preferably 2.5:4:1
Secondly, the first reactant liquor is placed at 45～60 DEG C, reacts 7～12 hours, obtain containing Isosorbide-5-Nitrae-bis-The reactant liquor of diethylin-2,3-butanediol.
Afterwards, the reactant liquor that contains Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol is carried out to reduced pressure concentration, gained is solidBody residue is dissolved in dimethyl carbonate, filters, and collects filtrate, then filtrate is carried out to reduced pressure concentration, obtainsIsosorbide-5-Nitrae-bis-diethylin-the 2,3-butanediol of purifying. Reduced pressure concentration for the first time in this step is in order to remove moistureAnd responseless diethylamine, after add dimethyl carbonate dissolved solid residue, Isosorbide-5-Nitrae-bis-diethylin-2,3-fourthGlycol is dissolved in dimethyl carbonate solvent, to remove unnecessary alkali, finally carries out reduced pressure concentration for the second time again,Remove dimethyl carbonate solvent.
Finally, in dimethyl carbonate, dissolve triethylamine and above-mentioned steps gained Isosorbide-5-Nitrae-bis-diethylin-2,3-Butanediol, obtains mixed liquor, after under nitrogen atmosphere, mixed liquor is cooled to 8～12 DEG C, then by methyl-propThe dimethyl carbonate lysate of alkene acyl chlorides is added in mixed liquor, stirring reaction 7～12 hours. Further,In the time that reaction temperature is 10 DEG C, show high response and high yield.
Dimethyl carbonate (dimethylcarbonate, DMC), has good solubility property, its molten, boiling pointNarrow range, surface tension is large, viscosity is low, medium circle electric constant is little, have simultaneously higher evaporating temperature andEvaporation rate faster, therefore can be used as low poison solvent for coatings industry and pharmaceuticals industry. Therefore, existIn above-mentioned preparation method, adopt dimethyl carbonate as solvent.
In above-mentioned steps, the example of alkali used includes, but not limited to organic or inorganic alkali, as NaOH(NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH)2), potassium tert-butoxide (t-BuOK),TMAH, sodium hydride (NaH), hydrofining (KH), calcium hydride (CaH2) and analog.In these alkali, NaOH and potassium hydroxide show high response and high yield.
After reaction finishes, what obtain is the reactant liquor that contains crosslinking agent, then, also can carry out crosslinking agentPurifying and recycling step:
The solution filter that gained is contained to crosslinking agent, collects filtrate, is oxidized after filtrate is removed to triethylamineAluminium column chromatography.
Step to the solution filter that contains crosslinking agent in above-mentioned steps, and carry out the step of alumina column chromatographySuddenly, can adopt conventional filtration and alumina column chromatography method, the parameter in these two processes is chosen as thisThose skilled in the art's routine is selected. The step of in above-mentioned steps, filtrate being removed to triethylamine, can adopt abilityThe removal method that field technique personnel know, for example, wash with water.
Crosslinking agent of the present invention has methacryl and two functional groups of diethyl amido, a side simultaneouslyFace, the former as with the cross-linking chemistry group of the hydroxyl effect of polyvinyl alcohol, crosslinkable forms with polyvinyl alcoholFor the polymer of skeleton, on the other hand, the latter can with CO2Effect, the polymer forming can be used as dioxyChange carbon responsive polymer.
The preserving type of the prepared crosslinking agent of the present invention does not have special restriction, can be dispersed in solventFor example, in (dimethyl carbonate), preserve with liquid form, also can preserve with solid form.
Photosynthesis-carbon dioxide response polymer of the present invention, is formed by polyvinyl alcohol and above-mentioned crosslinking agent reaction.
The preparation method of this polymer is preferably but be not limited to as follows:
(1) in toluene, crosslinking agent and initator are dissolved, obtain organic liquor, wherein, described initatorFor azodiisobutyronitrile, the mol ratio of described crosslinking agent and described initator is 10:1;
(2) polyvinyl alcohol is dissolved in the water, obtains the aqueous solution;
(3) by after organic liquor and aqueous solution, under nitrogen atmosphere, gained mixed liquor is heated to 80 DEG C,React 4 hours.
In following examples, reactant and product all adopt mass spectrum and nuclear magnetic resonance to analyze.
Embodiment 1:
The embodiment of the present invention 1 provides a kind of crosslinking agent, in accordance with the following steps preparation:
At (1) 0 DEG C, in deionized water, KOH (8.75g, 0.151mol) is dissolved into water (35mL)In, obtain aqueous slkali; Subsequently diethylamine (25mL, 0.242mol) is joined in aqueous slkali to 5～20After minute, more bromo-Isosorbide-5-Nitrae-bis-2,3-butanediol (15.1g, 0.0605mmol) is joined in aqueous slkali and is mixed,Obtain the first reactant liquor;
(2) the first reactant liquor is placed at 50 DEG C, reacts 7～12 hours, obtain containing Isosorbide-5-Nitrae-bis-diethylamineThe reactant liquor of base-2,3-butanediol;
(3) reactant liquor that contains Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol is carried out to reduced pressure concentration, gained is solidBody residue is dissolved in dimethyl carbonate (50ml), filters, and collect filtrate, then it is dense that filtrate is reduced pressureContract, obtain the Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol (7.62g, 54%) of purifying;
(4) in dimethyl carbonate, dissolve triethylamine (20mL) and step (3) gained Isosorbide-5-Nitrae-bis-diethylAmido-2,3-butanediol (6.9g, 30mmol), obtains mixed liquor, after under nitrogen atmosphere, mixed liquor is fallenWarm to 10 DEG C, then the dimethyl carbonate of methacrylic chloride (7.2mL, 74mmol) (50mL) is dissolvedLiquid is added in mixed liquor, stirring reaction 7～12 hours;
(5) by step (4) gained solution filter, collect filtrate, filtrate water washing is removed to triethylamineAfter carry out alumina column chromatography, obtain crosslinking agent product (8.9g, 81%).
Isosorbide-5-Nitrae-bis-diethylin-the 2,3-butanediol of step (3) gained purifying is analyzed, and result is as follows:
1HNMR(400MHz,CDCl3):δ3.77,2.71-2.57(m,12H),1.06(t,12H)；13CNMR(100MHz,CDCl3):δ68.8,56.4,47.3,11.6；HRMS(m/z):[M]+calcd.C12H28N2O2,232.2151,found232.2157。
Step (5) gained crosslinking agent product is analyzed, and result is as follows:
1HNMR(400MHz,CDCl3):δ6.17-6.14(m,4H),5.67(m,2H),3.75,2.68-2.59(m,12H),1.98(s,6H),1.06(t,12H)；
HRMSC20H36N2O4,calc.368.2675,found368.2668。
Embodiment 2:
The embodiment of the present invention 2 provides a kind of crosslinking agent, in accordance with the following steps preparation:
At (1) 0 DEG C, in deionized water, KOH (5.25g, 0.0906mol) is dissolved into water (35mL)In, obtain aqueous slkali; Subsequently diethylamine (12.5mL, 0.121mol) is joined in aqueous slkali to 5～20After minute, more bromo-Isosorbide-5-Nitrae-bis-2,3-butanediol (15.1g, 0.0605mmol) is joined in aqueous slkali and is mixed,Obtain the first reactant liquor;
(2) the first reactant liquor is placed at 45 DEG C, reacts 7～12 hours, obtain containing Isosorbide-5-Nitrae-bis-diethylamineThe reactant liquor of base-2,3-butanediol;
(3) reactant liquor that contains Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol is carried out to reduced pressure concentration, gained is solidBody residue is dissolved in dimethyl carbonate (50ml), filters, and collect filtrate, then it is dense that filtrate is reduced pressureContract, obtain the Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol (6.72g) of purifying;
(4) in dimethyl carbonate, dissolve triethylamine (20mL) and step (3) gained Isosorbide-5-Nitrae-bis-diethylAmido-2,3-butanediol (6.9g, 30mmol), obtains mixed liquor, after under nitrogen atmosphere, mixed liquor is fallenWarm to 8 DEG C, then the dimethyl carbonate of methacrylic chloride (7.2mL, 74mmol) (50mL) is dissolvedLiquid is added in mixed liquor, stirring reaction 7～12 hours.
(5) by step (4) gained solution filter, collect filtrate, filtrate water washing is removed to triethylamineAfter carry out alumina column chromatography, obtain crosslinking agent product (8.8g).
Embodiment 3:
The embodiment of the present invention 3 provides a kind of crosslinking agent, in accordance with the following steps preparation:
At (1) 0 DEG C, in deionized water, KOH (10.5g, 0.1812mol) is dissolved into water (35mL)In, obtain aqueous slkali; Subsequently diethylamine (32mL, 0.3mol) is joined in aqueous slkali to 5～20 pointsZhong Hou, more bromo-Isosorbide-5-Nitrae-bis-2,3-butanediol (15.1g, 0.0605mmol) is joined in aqueous slkali and mixed,Obtain the first reactant liquor;
(2) the first reactant liquor is placed at 60 DEG C, reacts 7～12 hours, obtain containing Isosorbide-5-Nitrae-bis-diethylamineThe reactant liquor of base-2,3-butanediol;
(3) reactant liquor that contains Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol is carried out to reduced pressure concentration, gained is solidBody residue is dissolved in dimethyl carbonate (50ml), filters, and collect filtrate, then it is dense that filtrate is reduced pressureContract, obtain the Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol (6.72g) of purifying;
(4) in dimethyl carbonate, dissolve triethylamine (20mL) and step (3) gained Isosorbide-5-Nitrae-bis-diethylAmido-2,3-butanediol (6.9g, 30mmol), obtains mixed liquor, after under nitrogen atmosphere, mixed liquor is fallenWarm to 12 DEG C, then the dimethyl carbonate of methacrylic chloride (7.2mL, 74mmol) (50mL) is dissolvedLiquid is added in mixed liquor, stirring reaction 7～12 hours.
(5) by step (4) gained solution filter, collect filtrate, filtrate water washing is removed to triethylamineAfter carry out alumina column chromatography, obtain crosslinking agent product (8.8g).
Embodiment 4:
The embodiment of the present invention 4 provides a kind of photosynthesis-carbon dioxide response polymer, in accordance with the following steps preparation:
(1) in toluene (4mL), by crosslinking agent (2.73g, 7.4mmol) and initator (12mg, 0.073Mmol) dissolve, obtain organic liquor, wherein, described initator is azodiisobutyronitrile (AIBN);
(2) by polyvinyl alcohol (87-89%hydrolyzed, averageMw124000-186000,0.4g)Be dissolved in the water, obtain the aqueous solution;
(3) by after organic liquor and aqueous solution, under nitrogen atmosphere, gained mixed liquor is heated to 80 DEG C,React 4 hours.
Step (4) products therefrom is analyzed under Electronic Speculum, and result as shown in Figure 3 and Figure 4.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all of the present inventionAny amendment of doing within spirit and principle, be equal to replacement and improvement etc., all should be included in guarantor of the present inventionWithin protecting scope.
Claims (10)
1. a crosslinking agent, is characterized in that, this crosslinking agent is the compound with structural formula (I),
2. the preparation method of crosslinking agent claimed in claim 1, is characterized in that, first, and in 45～60 DEG CUnder, under the existence of alkali, bromo-Isosorbide-5-Nitrae-bis-2,3-butanediol and excessive diethylamine are reacted to raw in polar solventBecome Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol; Then, at 8～12 DEG C, under the existence of triethylamine, willIsosorbide-5-Nitrae-bis-diethylin-2,3-butanediol reacts generation in Carbon Dioxide dimethyl ester with methacrylic chloride.
3. preparation method according to claim 2, is characterized in that, comprises the steps:
At (1) 0 DEG C, in deionized water, alkali is dissolved, obtain aqueous slkali; Subsequently diethylamine is addedIn aqueous slkali, after 5～20 minutes, more bromo-Isosorbide-5-Nitrae-bis-2,3-butanediol is joined in aqueous slkali and mixed,To the first reactant liquor;
(2) the first reactant liquor is placed at 45～60 DEG C, reacts 7～12 hours, obtain containing Isosorbide-5-Nitrae-bis-or twoThe reactant liquor of ethylamino--2,3-butanediol;
(3) reactant liquor that contains Isosorbide-5-Nitrae-bis-diethylin-2,3-butanediol is carried out to reduced pressure concentration, gained is solidBody residue is dissolved in dimethyl carbonate, filters, and collects filtrate, then filtrate is carried out to reduced pressure concentration, obtainsIsosorbide-5-Nitrae-bis-diethylin-the 2,3-butanediol of purifying;
(4) in dimethyl carbonate, dissolve triethylamine and step (3) gained Isosorbide-5-Nitrae-bis-diethylin-2,3-Butanediol, obtains mixed liquor, after under nitrogen atmosphere, mixed liquor is cooled to 8～12 DEG C, then by methyl-propThe dimethyl carbonate lysate of alkene acyl chlorides is added in mixed liquor, stirring reaction 7～12 hours.
4. preparation method according to claim 3, is characterized in that, also wraps afterwards in step (4)Draw together following steps:
(5) by step (4) gained solution filter, collect filtrate, after being removed to triethylamine, filtrate carries out oxygenChange aluminium column chromatography.
5. according to the preparation method described in claim 2 to 5 any one, it is characterized in that, described alkali is selected fromNaOH, potassium hydroxide, calcium hydroxide, potassium tert-butoxide, TMAH, sodium hydride or hydrogenationPotassium.
6. preparation method according to claim 3, is characterized in that, the reaction temperature of step (2)It is 50 DEG C. The reaction temperature of step (4) is 10 DEG C.
7. preparation method according to claim 3, is characterized in that, the alkali, two in step (1)The mol ratio of ethamine and the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-is (1.5～3): (2～5): 1, wherein, step (1)In the mol ratio of alkali, diethylamine and the bromo-2,3-butanediol of Isosorbide-5-Nitrae-bis-be preferably 2.5:4:1.
8. crosslinking agent claimed in claim 1 is in the purposes of preparing in photosynthesis-carbon dioxide response polymer.
9. a photosynthesis-carbon dioxide response polymer, is characterized in that, described in polyvinyl alcohol and claim 1Crosslinking agent reaction form.
10. polymer according to claim 9, is characterized in that, preparation method's bag of this polymerDraw together following steps:
(1) in toluene, crosslinking agent and initator are dissolved, obtain organic liquor, wherein, described initatorFor azodiisobutyronitrile, the mol ratio of described crosslinking agent and described initator is 10:1;
(2) polyvinyl alcohol is dissolved in the water, obtains the aqueous solution;
(3), by after organic liquor and aqueous solution, under nitrogen atmosphere, gained mixed liquor is heated to 80 DEG C, reaction4 hours.
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| CN109485773A (en) * | 2018-09-29 | 2019-03-19 | 江汉大学 | One kind having CO2Oil-absorbing resin of stimuli responsive and preparation method thereof |
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