CN109868066A - Abietyl CO2/N2Response type surfactant and preparation method and purposes - Google Patents

Abstract

The present invention discloses a kind of abietyl CO₂/N₂Response type polymerisable surfactant is reacted with glycidyl methacrylate (GMA) by maleopimaric acid and introduces polymerisable monomer, then with N, N- dimethyl -1,3- propane diamine carries out imidization reaction introducing can be to CO₂The tertiary amine group of response.The surfactant is to CO₂/N₂With response performance, it is passed through CO₂Rear solution shows faintly acid and tertiary amine is made to protonate to form tertiary ammonium salt and positively charged become water-soluble cationic form；It is passed through N₂Drive CO out of₂Positively charged tertiary ammonium salt deprotonation is restored to initial tertiary amine state that cannot be water-soluble afterwards, has response invertibity well.Invention additionally discloses the emulsifiability of such surfactant and dispersion performance, the Pickering lotion and carbon nano tube dispersion liquid prepared by the surfactant is to CO₂/N₂Equally there is good responsiveness, end group double bond can prepare high molecular surfactant by polymerization reaction.

Description

Abietyl CO2/N2Response type surfactant and preparation method and purposes

Technical field

The present invention relates to a kind of green surfactant more particularly to a kind of abietyl CO₂/N₂The polymerizable surface of response type Activating agent, preparation method and the application in fields such as emulsion dispersions.

Background technique

Carbon nanotube is received extensive attention because having unique thermal stability, electric property and mechanical performance, still Strong π-π interaction and Van der Waals force cause it easily to reunite between carbon nanotube molecule, so limiting carbon nanotube Extensive use.Therefore there is an urgent need to effective methods to carry out dispersing Nano carbon tubes.Amphipathic molecule is commonly used for dispersing carbon nanometer Pipe, such as surfactant, DNA, ionic liquid, grease or polymer.When carbon nanotube is used in drug or biochemistry When equal fields, " intelligent " surface need to be often modified to meet the responsiveness to environment, so carbon nanotube is by response type table Face activating agent has obtained extensive concern by non-covalent bond modification, and the carbon nanotube of reunion can not only be dispersed but also be had Certain " intelligence " can also protect the original excellent performance of carbon nanotube by the way of this non-covalent bond.

In food, the fields such as cosmetics often need lotion that can exist steadily in the long term, but are recovering the oil, emulsion polymerization etc. Field just needs to be demulsified after often needing lotion to be only stabilized the regular hour.So lotion how to be allowed to be stabilized and quickly Controllably become research hotspot between demulsification.

Response type surfactant with surface-active and can not have between surface-active under extraneous stimulation Carry out reversible transformation.The difference of mechanism according to response, response type surfactant are divided into two major classes, and one kind is to electrification It learns stimulation and generates responsiveness for example, pH, CO₂, reductant-oxidant etc., another kind of is to stimulate physical chemistry to generate responsiveness example Such as, light, heat and magnetic field etc..CO₂As a kind of environmentally friendly, nontoxic, the stimulating factor of cheap and easy removing and Obtain extensive concern.

However, in existing report, most of CO₂Response type surfactant is all or with conventional petroleum primary surface activity Agent is raw material, this also greatly limits the type of surfactant not only to environmental danger.

With the continuous enhancing of environmental consciousness, there is an urgent need to develop environmental type responsiveness surfactant, with natural Resource replaces fossil resources.Rosin is a kind of natural resin by pine tree naturally secret, abundance, cheap and have Reproducibility.The tricyclic rigid backbone of rosin has very strong hydrophobicity, it is possible to its active group carboxyl and double bond into Row chemical modification introduces the excellent surfactant of hydrophilic radical processability, has had much prepare by raw material of rosin at present Surfactant report, but abietyl response type surfactant research is also fewer, so this research is with rosin Response type surfactant is prepared for raw material and is used to prepare response type Pickering lotion and the dispersion of response type carbon nanotube Liquid.

Summary of the invention

The purpose of the present invention is to provide a kind of abietyl CO₂/N₂Response type polymerisable surfactant, and its preparation side Method and application.The surfactant is using biomass resource rosin as raw material, to CO₂/N₂With good responsiveness.

The ternary phenanthrene skeleton structure of rosin has very strong hydrophobicity, and modified gained surfactant has good table Face activity, lower critical micelle concentration, better emulsifiability, MPAGN are dissolved into CO₂Aqueous solution becomes cationic bicarbonate After salt with nano silica by electrostatic interaction in conjunction with prepare CO under high shear conditions₂/N₂Responsiveness Pickering cream Liquid.Gained Pickering lotion has good stability, and N is passed through into lotion at 60 DEG C₂, stable lotion can be at once It is demulsified, is passed through CO after demulsification again₂It is clipped to form stable lotion again, partial size with it is preceding primary almost the same.This Outside, water phase after demulsification emulsifiable new oily phase after collecting, partial size with emulsify for the first time it is almost the same, so the response type surface Activating agent can reuse.

The ternary phenanthrene skeleton structure of rosin, can be generated between carbon nanotube be similar to π-accumulation interaction force from And there is good dispersion performance to carbon nanotube.MPAGN is dissolved into CO₂After obtaining cationic surfactant in aqueous solution Initiator is added into dispersion liquid and carries out free radical polymerization in situ, so that high molecular surfactant is wound for dispersing Nano carbon tubes To carbon nano tube surface, by electrostatic repulsion and intermolecular force by stable dispersion between carbon nanotube.At 40 ~ 60 DEG C N is passed through into dispersion liquid₂, carbon nanotube settles from solution, is passed through CO again at room temperature₂It only need to gently shake afterwards several It is secondary to be dispersed back into aqueous solution, no longer need to ultrasound.

The present invention adopts the following technical scheme: a kind of CO₂/N₂Response type polymerisable surfactant, product structure formula is such as Under:

The preparation method of the surfactant, the first step, rosin and maleic anhydride carry out addition reaction and maleopimaric acid are made；The Two steps, maleopimaric acid occur esterification by ring opening with GMA and react generation MPAG；Third step, MPAG and N, N- dimethyl -1,3- the third two Amine carries out imidization reaction, obtains target product MPAGN.

Wherein rosin and maleic anhydride the mass ratio of the material are 1:(1 ~ 1.5), such as ratio can choose 1:1,1:1.1,1: 1.2,1:1.3,1:1.4,1:1.5；Acetic acid makees solvent, and 120 ~ 140 DEG C of reaction temperature, such as 120 DEG C, 130 DEG C, 140 DEG C；Reaction 3 ~ 6h of time, such as 3h, 4h, 5h, 6h.

The mass ratio of the material of maleopimaric acid and GMA are 1:(1 ~ 1.2), such as ratio selection 1:1,1:1.1,1:1.2；It urges The amount of agent triethylamine is 0.5 ~ 2wt% of reactant gross mass, such as 0.5%, 1%, 1.5%, 2%；The amount of hydroquinone of polymerization retarder For 0.2 ~ 0.5wt% of reactant gross mass, such as 0.2%, 0.3%, 0.4%, 0.5%；Toluene makees solvent, and reaction temperature is 80 ~ 120 DEG C, such as 80 DEG C, 100 DEG C, 120 DEG C；6 ~ 8h of reaction time, such as 6h, 7h, 8h, obtain MPAG.

The ratio between amount of substance of MPAG and N, N- dimethyl -1,3- propane diamine is 1:(1 ~ 5), such as ratio can choose 1: 1,1:1.1,1:1.2,1:1.3,1:1.4,1:1.5；Ethanol as solvent, reaction temperature are 60 ~ 80 DEG C, such as 60 DEG C, 70 DEG C, and 80 ℃；4 ~ 6h of reaction time, such as 4h, 5h, 6h, obtain MPAGN, are passed through CO₂/N₂, the pH and conductivity of solution can follow Ring variation.

MPAGN is dissolved into CO₂Aqueous solution becomes to pass through electrostatic interaction knot with nano silica after cationic bicarbonate Conjunction prepares CO under high shear conditions₂/N₂Response type Pickering lotion, gained Pickering lotion have steady well It is qualitative, at 40 ~ 60 DEG C, such as 40 DEG C, 50 DEG C, 60 DEG C are passed through N into lotion₂, demulsification can immediately occurred in stable lotion, broken CO is passed through after cream again₂It is clipped to form stable lotion again, partial size with it is preceding primary almost the same.In addition, after demulsification Water phase can be used for emulsifying new oily phase after collecting, partial size with emulsify for the first time it is almost the same, so the response type surfactant It can reuse.

MPAGN is dissolved into CO₂Dispersing Nano carbon tubes after aqueous solution, into dispersion liquid be added initiator V50 1wt% ~ 3wt%, such as 1%, 2%, 3%, free radical polymerization in situ is carried out, so that high molecular surfactant is wound into carbon nano tube surface, The carbon nano tube dispersion liquid of stable homogeneous is obtained, then at 40 ~ 60 DEG C, such as 40 DEG C, 50 DEG C, 60 DEG C, lead into dispersion liquid Enter N₂, carbon nanotube settles from solution, is passed through CO again at room temperature₂Only need to gently shake afterwards several times can be again It is distributed in aqueous solution, no longer needs to ultrasound.

The raw material of such surfactant is natural resources rosin, meets the theory of Green Sustainable, introduces rosin Ternary phenanthrene skeleton structure, as emulsifier preparation Pickering lotion have good emulsifiability, as dispersing agent disperse Carbon nanotube has good dispersion stabilization, introduces tertiary amine group to CO₂/N₂With good responsiveness, lead to after introducing double bond It crosses the obtained high molecular surfactant of free radical polymerization in situ and is wound into carbon nano tube surface, there is good redispersibility.

The present invention obtains following technical effect:

1. the present invention combines the design feature of rosin, by D-A addition, esterification, the methods of imidizate has synthesized a kind of rosin Base CO₂/N₂Response type polymerisable surfactant MPAGN；MPAGN cannot dissolve in water, CO₂H is formed after being passed through in water₂CO₃, MPAGN is protonated, the cationic carbonate for being dissolved in water is formed, is passed through N₂CO afterwards₂ It is discharged, the MPAGN of protonation is returned to most Tertiary amine state just not soluble in water, this process can be repeated.

2.MPAGN prepares CO as emulsifier₂/N₂Response type Pickering lotion, gained Pickering lotion have Good stability is passed through N into lotion at 60 DEG C₂, stable lotion can immediately occurred demulsification, be passed through CO after demulsification again₂ It is clipped to form stable lotion again, partial size with it is preceding primary almost the same.In addition, the water phase after demulsification is emulsifiable after collecting New oily phase, partial size with first time emulsify it is almost the same, so the response type surfactant can reuse.

3. MPAGN is dissolved into CO₂Dispersing Nano carbon tubes add initiation after aqueous solution forms cationic surfactant Agent V50 carries out free radical polymerization in situ, and high molecular surfactant is wound into carbon nano tube surface, passes through between carbon nanotube quiet Electric repulsion and intermolecular force and the carbon nano tube dispersion liquid of stable homogeneous is obtained by stable dispersion, at 40 ~ 60 DEG C to point N is passed through in dispersion liquid₂, carbon nanotube settles from solution, is passed through CO again at room temperature₂It only need to gently shake several times just afterwards It can be dispersed back into aqueous solution, no longer need to ultrasound.

Detailed description of the invention

Attached drawing 1 is MPAGN nuclear magnetic spectrogram；

Attached drawing 2 is MPAGN to CO₂/N₂Response Mechanism figure；

Attached drawing 3 is MPAGN with CO₂/N₂The alternately circulation change of the pH being passed through and conductivity；

Attached drawing 4 is gained Pickering lotion to CO₂/N₂Respond invertibity；

Attached drawing 5 is gained carbon nano tube dispersion liquid to CO₂/N₂Respond invertibity；

Specific embodiment

Embodiment 1

A kind of abietyl CO₂/N₂Response type polymerisable surfactant, the structural formula of product are as follows:

Embodiment 2

Abietyl CO₂/N₂The synthesis of response type polymerisable surfactant the following steps are included:

100g(0.33mol, abietic acid, neoabietic acid, palustric acid total amount are calculated by 80%, 0.265mol) masson pine rosin, 35g 100g glacial acetic acid is added in (0.357mol) maleic anhydride, 40g acetic acid, 140 DEG C of reaction 4h after cooling, crystallisation by cooling is filtered, obtained To maleopimaric acid.

Take 40g maleopimaric acid and 14.2g GMA in temperature sleeves, agitating device, the four-hole boiling flask of reflux unit In, appropriate hydroquinone is added thereto as polymerization inhibitor (amount of hydroquinone account for about reactant gross mass 0.2 ~ 0.5%), Triethylamine is as catalyst (amount of triethylamine account for about reactant gross mass 0.2 ~ 0.5%), in toluene solvant, back flow reaction Solvent rotary evaporation is obtained MPAG after completion of the reaction by 7h

Above-mentioned reaction product is placed in three-necked flask, is dissolved in ethanol, after stirring 0.5h at 85 DEG C, by N, N- diformazan Base -1,3- propane diamine dissolves in a solvent, is added dropwise in reactor, continues to stir 5h after being added dropwise, solvent be steamed, slightly Product obtains product MPAGN through chromatographic column purification (methanol: methylene chloride 1:9), and structure determines (attached drawing through nmr spectrum 1).

Embodiment 3

Surfactant is to CO₂/N₂With good response effect (attached drawing 2), by MPAGN electrical conductivity of solution and pH can Reversal judgement gained MPAGN is to CO₂/N₂Responsiveness.CO₂It is dissolved in aqueous solution and forms H₂CO₃Weak acid solution (pH=5.2), leads The protonation of tertiary amine group is caused, generating electrically charged cationic surfactant makes conductivity rise to about 340 μ S/cm.When 60 N is passed through at DEG C₂Drive CO out of₂Afterwards, solution faintly acid disappears (pH=7.4), and electrically charged cationic surfactant deprotonation is returned To initial tertiary amine group state, conductivity is made to be reduced to about 177 μ S/cm, when being passed through CO again₂Afterwards, conductivity rises to again About 340 S/cm(pH=5.2 μ), this process, which may be repeated several times, illustrates MPAGN to CO₂/N₂With good responsiveness (attached drawing 3).

Embodiment 4

Abietyl CO₂/N₂Response type polymerisable surfactant is used to prepare Pickering lotion: being passed through CO₂Lead to tertiary amine groups The protonation of group generates electrically charged cationic surfactant, Nano-meter SiO_2₂It is mutually tied with cationic MPAGN by electrostatic interaction Close preparation Pickering lotion.0.5wt%SiO₂ (relative to water phase) is dispersed in the CO of the MPAGN of various concentration₂In aqueous solution If 0.05mM, 0.1mM, 0.5mM etc. take 7mL water phase that 7mL atoleine is added, high shear 5min, is obtained at 1100rpm Pickering lotion.Particle diameter distribution does not have significant change to prove gained emulsion intercalation method after 1 day and after 7 days；To body at 60 DEG C N is passed through in system₂, electrically charged cationic surfactant deprotonation returns to initial tertiary amine group state, SiO₂It is living with surface Property agent between electrostatic interaction disappear, lotion is demulsified rapidly；It is passed through CO again₂And it is obtained again after high shear stable Pickering lotion, and the particle diameter distribution of gained lotion does not have variation to illustrate prepared by MPAGN substantially for the first time and after response Pickering lotion is to CO₂/N₂Equally there is good responsiveness；Water phase is collected after emulsion breaking, new 7mL is added again Same available stable Pickering lotion and particle diameter distribution does not change substantially with last after atoleine is clipped MPAGN can recycle (attached drawing 4) after proving demulsification.

Embodiment 5

Abietyl CO₂/N₂Response type polymerisable surfactant is used to prepare carbon nano tube dispersion liquid: 0.08g MPAGN adds water To 24mL, CO is passed through into aqueous solution₂MPAGN is added after completely dissolution 0.008g single-walled carbon nanotube (SWNTs), ultrasound It is centrifuged 10min at 8000rpm after 20min, obtains the SWNTs dispersion liquid of stable homogeneous.3%V50 is added into SWNTs to cause Agent saves 8h at 50 DEG C and carries out free radical polymerization in situ.N is passed through into system at 60 DEG C₂, carbon nanotube precipitates from solution Out, it is passed through CO again at room temperature₂Only need to gently shake afterwards can be dispersed back into aqueous solution several times, no longer need to ultrasound The operation can be repeated several times without significant change, pass through the UV absorption of dispersion liquid after comparison preparation for the first time and redisperse Peak proves that gained dispersion liquid has good redispersibility (attached drawing 5).

Claims (4)

1. abietyl CO₂/N₂Response type surfactant, structural formula are as follows:

。

2. a kind of abietyl CO according to claim 1₂/N₂The preparation method of response type surfactant: the first step, pine It is fragrant to carry out addition reaction with maleic anhydride maleopimaric acid is made, wherein rosin and maleic anhydride the mass ratio of the material be 1:(1 ~ 1.5), acetic acid makees solvent, and 120 ~ 140 DEG C of 3 ~ 6h of reaction are added in a large amount of acetic acid after cooling, filter after crystallisation by cooling, obtain horse Carry out pimaric acid；Second step, maleopimaric acid occur esterification by ring opening with GMA and react generation MPAG；Wherein maleopimaric acid and GMA The mass ratio of the material is 1:(1 ~ 1.2), the amount of catalyst of triethylamine is 0.5 ~ 2wt% of reactant gross mass, hydroquinone of polymerization retarder Amount be reactant gross mass 0.2 ~ 0.5wt%, toluene makees solvent, and reaction temperature is 80 ~ 120 DEG C, and 6 ~ 8h of reaction is obtained MPAG；Third step, MPAG in anhydrous ethanol solvent with N, N- dimethyl -1,3- propane diamine carry out imidization reaction obtain MPAGN, wherein MPAG and N, the ratio between amount of substance of N- dimethyl -1,3- propane diamine are 1:(1 ~ 5), ethanol as solvent, reaction Temperature is 60 ~ 80 DEG C, 4 ~ 6h of reaction time.

3. abietyl CO according to claim 1₂/N₂Response type surfactant can be used as emulsifier and prepare response type Pickering lotion.0.1 ~ 1wt% (relative to water phase) Nano-meter SiO_2₂It is dispersed in the MPAGN CO of various concentration₂In aqueous solution, Isometric water phase and oil are mutually in 8000 ~ 15000rpm high shear, 3 ~ 10min；Gained lotion can be stabilized, but at 40 ~ 60 DEG C Under be passed through N₂Demulsification can immediately occurred in lotion afterwards, be passed through CO after demulsification again₂It is clipped to form stable lotion, partial size again With it is preceding primary almost the same；In addition, the water phase after demulsification can be used for emulsifying new oily phase, partial size and first time emulsified base after collecting This is consistent, which can reuse.

4. abietyl CO according to claim 1₂/N₂Response type surfactant can be used as dispersing agent dispersion carbon nanometer Pipe: 50 ~ 100mg MPAGN is dissolved into 20 ~ 30 mL CO₂Disperse 5 ~ 10mg carbon nanotube, ultrasound as dispersing agent after aqueous solution After dispersing 10 ~ 30min, 5 ~ 20min is centrifuged at 5000 ~ 8000rpm and obtains carbon nano tube dispersion liquid, initiator 1 ~ 3 is added Wt% V50 initiator reacts 6 ~ 10h at 40 ~ 60 DEG C and high molecular surfactant is made to be wound into carbon nano tube surface, obtains The carbon nano tube dispersion liquid of stable homogeneous is passed through N into dispersion liquid then at 40 ~ 60 DEG C₂, carbon nanotube from solution sink Drop comes out, and is passed through CO again at room temperature₂Only need to gently shake afterwards can be dispersed back into aqueous solution several times, no longer need to surpass Sound.