CN107840965A - A kind of preparation method of the amphipathic polymer of long branched chain structure - Google Patents
A kind of preparation method of the amphipathic polymer of long branched chain structure Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the amphipathic polymer of long branched chain structure, the amphipathic polymer is by the terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two in mass ratio 1：2~1：5 reactions obtain.In the polymer chain structure of the long-chain branch amphipathic polymer of the present invention, there is long branched chain structure, action site is more.And contain this active group of benzene sulfonic acid base, the reaction compartment of emulsifying agent has further been expanded, has realized preferable emulsifying effectiveness, therefore the heat-resistant salt-resistant performance of its solution is good, surface and interface activity is strong.
Description
Technical field
The present invention relates to a kind of preparation method of the amphipathic polymer of long branched chain structure, belongs to water soluble polymer technology neck
Domain.
Background technology
Due to amphiphilic structure and molecular weight it is higher, can effectively be adsorbed on surface and interface, macromolecule emulsifier has
Compared with the more preferable emulsifiability of Small molecular surfactant, such as：Chinese patent document CN103721627A (application numbers：
201310685017.0) a kind of thermosensitive miktoarm star high molecular emulsifier and preparation method thereof, the macromolecule emulsifier be by
Two kinds of different monomers polymerize RAFT methods by reversible addion-fragmentation chain transfer respectively, form high score of the degree of polymerization 60~150
Sub- linear arms, one of which macromolecule arm have thermal sensitivity, and another kind is water miscible, then using both macromolecule arms as tune
Control reagent and core crosslinking star gear transmission emulsifying agent is formed by heteropolymerization crosslinking agent.Based on above-mentioned characteristic, various macromolecule latexes
Agent is increasingly being applied in thickened oil recovery, is reduced viscosity of thickened oil by emulsification, is improved its mobility, make it easier to
Exploitation.
However, amphipathic polymer is applied to the problem of universality is not strong be present in thickened oil recovery.Such as：Chinese patent document
CN104558405A (application numbers：201510017630.4) a kind of preparation method of amphiprotic polyacrylamide is disclosed, belong to high
Molecular chemistry polymerisation field.The method prepared using rapid polymerization under normal temperature, by acrylamide and anions and canons monomer with
And emulsifying agent, hexamethylene, water are well mixed and are configured to transparent microemulsion system, are then reacted under normal temperature by thermal-initiated polymerization
Obtain amphiphilic polymers.To meet that just needs develop a variety of amphipathic polymers to different use demands, conventional polymer emulsifying agent is past
It is past to start with from the change of amphiphilic composition, therefore development cost is higher, the cycle is longer.And traditional macromolecule emulsifier salt tolerant is resistance to
Warm nature can need further to improve, while lack active group so that action site is few in emulsifying agent macromolecule, emulsifier solution
Surface and interface activity deficiency, influence emulsifying effectiveness.
Therefore, development cost is cheap, the macromolecule emulsifier in molecule more than action site is asked as technology urgently to be resolved hurrily
Topic.
The content of the invention
In view of the deficienciess of the prior art, especially traditional macromolecule emulsifier heat-resistant salt-resistant performance needs further
Improve, while lack active group so that action site is few in emulsifying agent macromolecule, the defects of influenceing emulsifying effectiveness, the present invention
From the angle of adjustment polymer chain structure, there is provided a kind of preparation method of the amphipathic polymer of long branched chain structure.
Technical scheme is as follows：
A kind of amphipathic polymer of long branched chain structure, described amphipathic polymer by the terpolymer containing epoxy radicals and
Amino End Group two-spot copolymer reaction obtains；The mass ratio of terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two is 1:
2~1:5.
, according to the invention it is preferred to, described amphipathic polymer number-average molecular weight is 6.419 × 105~1.024 × 106g/
mol。
, according to the invention it is preferred to, described amphipathic polymer is in shearing rate 6.25s-1Down cut viscosity be 11.61~
34.07mPa.s。
, according to the invention it is preferred to, the terpolymer containing epoxy radicals by acrylamide, 2- acrylamidos-
2- methyl propane sulfonic acids, GMA copolyreaction are made；It is further preferred that copolyreaction is in organic solvent
Middle progress, it is furthermore preferred that organic solvent is dimethyl sulfoxide (DMSO).The copolyreaction can be Raolical polymerizable.
, according to the invention it is preferred to, in the copolyreaction of the terpolymer containing epoxy radicals, acrylamide, 2-
Acrylamide-2-methylpro panesulfonic acid, the molfraction ratio of GMA are (79.0~79.9)：20：
(1.0~0.1), the monomer populations of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and GMA
The mass fraction for accounting for reaction system is 10~20%, concretely 10%, 15%, 20%；
Preferably, the copolyreaction of the terpolymer containing epoxy radicals is reacted under initiator initiation, is entered
One step is preferable, and initiator is azodiisobutyronitrile, and the mass fraction that initiator accounts for reaction system is 0.1~0.5%, specifically may be used
For 0.1%, 0.2%, 0.5%；
Preferably, the copolyreaction temperature of the terpolymer containing epoxy radicals is 60~70 DEG C, concretely 60
℃、65℃、70℃；The copolyreaction time is 6~15h, concretely 6h, 10h, 15h.
, according to the invention it is preferred to, the membered copolymer of Amino End Group two is by acrylamide, SSS, sulfydryl second
Amine copolymer is made.It is further preferred that it is made by aqueous free radical copolyreaction.
, according to the invention it is preferred to, in the aqueous free radical copolymerization, acrylamide, mole of SSS
Portion rate is (90.0~50.0):(10.0~50.0), more preferably 80:20, acrylamide and SSS
The mass fraction that monomer populations account for reaction system is 15~25%, further preferred 20%；
Preferably, the quality of mercaptoethylmaine accounts for the 0.3~1% of acrylamide and SSS gross mass.
, according to the invention it is preferred to, in the aqueous free radical copolymerization, reacted under initiator initiation, enter one
Step is preferable, and initiator is azo diisobutyl amidine hydrochloride, and the mass fraction that initiator accounts for reaction system is 0.5~1.0%,
Concretely 0.5%, 1.0%.
, according to the invention it is preferred to, the aqueous free radical co-polymerization temperature be 50~60 DEG C, concretely 50 DEG C,
55℃、60℃；The aqueous free radical combined polymerization time is 10~15h, concretely 10h, 12h, 15h.
According to the present invention, the preparation method of the long-chain branch amphipathic polymer, including：
By the terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two, the hybrid reaction in water produces.
According to the preparation method of long-chain branch amphipathic polymer of the present invention, it is preferred that the terpolymer containing epoxy radicals and
The mass ratio of the membered copolymer of Amino End Group two is 1:2~1:5；Preferably, the reaction time is 10~15h.
The amphipathic polymer of the long branched chain structure of the present invention has following structure：
According to the present invention, application of the above-mentioned long-chain branch amphipathic polymer in emulsified viscous oil.
A kind of emulsified viscous oil liquid, the emulsified viscous oil liquid include above-mentioned long-chain branch amphipathic polymer.
According to the emulsified viscous oil liquid of the present invention, it is preferred that the emulsified viscous oil liquid includes emulsifier aqueous solution and viscous crude, emulsification
The agent aqueous solution is 3 with viscous crude volume ratio:(5~10), further preferred 3:7.
According to the emulsified viscous oil liquid of the present invention, it is preferred that described emulsifier aqueous solution concentration is 0.5~5.0mg/mL,
Concretely 0.5mg/mL, 1.0mg/mL, 1.5mg/mL, 2.0mg/mL, 5.0mg/mL；
Preferably, described viscosity of thickened oil is 1300~15000mPa.s.
According to the present invention, the preparation method of above-mentioned emulsified viscous oil liquid, including：
Emulsifier aqueous solution is stirred with viscous crude and produced.Preferably, the volume ratio of emulsifier aqueous solution and viscous crude is
3:(5~10), further preferred 3:7；Temperature is stirred as 40~60 DEG C, further preferred 50 DEG C.
Beneficial effects of the present invention are as follows：
1st, the long-chain branch amphipathic polymer in the present invention is low using common cheap raw material, production cost.
2nd, in the polymer chain structure of long-chain branch amphipathic polymer of the invention, there is long branched chain structure, action site is more.
And contain this active group of benzene sulfonic acid base, further expand the reaction compartment of emulsifying agent.Therefore its solution is resistance to
Warm salt resistant character is good, and surface and interface activity is strong.At room temperature, such amphipathic polymer aqueous solution can be realized when concentration is 2.0mg/mL
Surface tension is down to 37.41mN/m, and the interfacial tension between viscous crude then can as little as 0.002mN/m.With the 0.1mol/L under concentration
The minimum reachable 32.07mN/m of NaCl solution surface tension.When being warming up to 60 DEG C, the surface tension with concentration of aqueous solution further drops
To 31.22mN/m, 0.1mol/L NaCl solutions surface tension then as little as 27.72mN/m.
3rd, long-chain branch amphipathic polymer of the invention realizes preferable emulsifying effectiveness, and concentration is that 2.0mg/mL amphiphilic gathers
The emulsifiable viscous crude of the compound aqueous solution forms the homogeneous latex emulsion of as little as 5 μm of size droplet diameter, and prepared with 10000ppm NaCl solutions
The emulsifiable viscous crude of the emulsifier salt solution forms the homogeneous latex emulsion of as little as 3.5 μm of size droplet diameter, and simple production process, in viscous crude
The fields such as exploitation have good application value.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the terpolymer containing epoxy radicals in the embodiment of the present invention 1.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of Amino End Group two-spot copolymer in the embodiment of the present invention 1.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of long-chain branch amphipathic polymer in the embodiment of the present invention 1.
Embodiment
Below by specific embodiment, the invention will be further described, but not limited to this.
It is experimentally conventional method unless otherwise specified in following embodiments.
The raw material such as agents useful for same can be obtained by commercial sources unless otherwise specified in following embodiments.
Embodiment 1
The preparation of terpolymer containing epoxy radicals：By acrylamide 2.835g, 2- acrylamido -2- methyl-prop sulphurs
Sour 2.093g, GMA 0.069mL, which are dissolved in 45mL dimethyl sulfoxide (DMSO)s, carries out free radicals copolymerization reaction,
Acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, the molfraction ratio of GMA are 79.0:20:
1.0, monomer mass fraction is 10%.Initiator is azodiisobutyronitrile 0.025g, mass fraction 0.5%, and reaction temperature is
65 DEG C, reaction time 10h.Polymer proton nmr spectra is shown in accompanying drawing 1.
The preparation of the membered copolymer of Amino End Group two：By acrylamide 5.796g, SSS 4.204g, mercaptoethylmaine
0.050g, which is dissolved in 50mL water, carries out free radicals copolymerization reaction, and acrylamide, the molfraction ratio of SSS are 80:
20, monomer mass fraction is 20%.Initiator is azo diisobutyl amidine hydrochloride, mass fraction 0.5%, and reaction temperature is
55 DEG C, reaction time 12h.The proton nmr spectra of polymer is shown in accompanying drawing 2.
Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two are 1 in mass ratio:5 mix in water, room temperature
12h is reacted, obtains long-chain branch amphipathic polymer.Polymer proton nmr spectra is shown in accompanying drawing 3.
It is 3 by volume:7, be by emulsifier aqueous solution and viscosity that long-chain branch amphipathic polymer concentration is 2.0mg/mL
1300mPa.s viscous crude mixing, 50 DEG C of stirrings form emulsified viscous oil liquid.
Embodiment 2
The preparation of terpolymer containing epoxy radicals：By acrylamide 2.852g, 2- acrylamido -2- methyl-prop sulphurs
Sour 2.097g, GMA 0.048mL, which are dissolved in 45mL dimethyl sulfoxide (DMSO)s, carries out free radicals copolymerization reaction,
Acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, the molfraction ratio of GMA are 79.3:20:
0.7, monomer mass fraction is 10%.Initiator is azodiisobutyronitrile 0.025g, mass fraction 0.5%, and reaction temperature is
65 DEG C, reaction time 10h.
The preparation of the membered copolymer of Amino End Group two：By acrylamide 5.796g, SSS 4.204g, mercaptoethylmaine
0.050g, which is dissolved in 50mL water, carries out free radicals copolymerization reaction, and acrylamide, the molfraction ratio of SSS are 80:
20, monomer mass fraction is 20%.Initiator is azo diisobutyl amidine hydrochloride, mass fraction 0.5%, and reaction temperature is
55 DEG C, reaction time 12h.
Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two are 1 in mass ratio:5 mix in water, room temperature
12h is reacted, obtains long-chain branch amphipathic polymer.
It is 3 by volume:7, by the emulsifier aqueous solution and viscosity that long-chain branch macromolecule emulsion agent concentration is 2.0mg/mL
Mixed for 1300mPa.s viscous crude, 50 DEG C of stirrings form emulsified viscous oil liquid.
Embodiment 3
The preparation of terpolymer containing epoxy radicals：By acrylamide 2.863g, 2- acrylamido -2- methyl-prop sulphurs
Sour 2.100g, GMA 0.035mL, which are dissolved in 45mL dimethyl sulfoxide (DMSO)s, carries out free radicals copolymerization reaction,
Acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, the molfraction ratio of GMA are 79.5:20:
0.5, monomer mass fraction is 10%.Initiator is azodiisobutyronitrile 0.025g, mass fraction 0.5%, and reaction temperature is
65 DEG C, reaction time 10h.
The preparation of the membered copolymer of Amino End Group two：By acrylamide 5.795g, SSS 4.204g, mercaptoethylmaine
0.050g, which is dissolved in 50mL water, carries out free radicals copolymerization reaction, and acrylamide, the molfraction ratio of SSS are 80:
20, monomer mass fraction is 20%.Initiator is azo diisobutyl amidine hydrochloride, mass fraction 0.5%, and reaction temperature is
55 DEG C, reaction time 12h.
Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two are 1 in mass ratio:5 mix in water, room temperature
12h is reacted, obtains long-chain branch amphipathic polymer.
It is 3 by volume:5, be by emulsifier aqueous solution and viscosity that long-chain branch amphipathic polymer concentration is 2.0mg/mL
1300mPa.s viscous crude mixing, 50 DEG C of stirrings form emulsified viscous oil liquid.
Embodiment 4
The preparation of terpolymer containing epoxy radicals：By acrylamide 2.875g, 2- acrylamido -2- methyl-prop sulphurs
Sour 2.103g, GMA 0.022mL, which are dissolved in 45mL dimethyl sulfoxide (DMSO)s, carries out free radicals copolymerization reaction,
Acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, the molfraction ratio of GMA are 79.7:20:
0.3, monomer mass fraction is 10%.Initiator is azodiisobutyronitrile 0.025g, mass fraction 0.5%, and reaction temperature is
65 DEG C, reaction time 10h.
The preparation of the membered copolymer of Amino End Group two：By acrylamide 5.796g, SSS 4.205g, mercaptoethylmaine
0.050g, which is dissolved in 50mL water, carries out free radicals copolymerization reaction, and acrylamide, the molfraction ratio of SSS are 80:
20, monomer mass fraction is 20%.Initiator is azo diisobutyl amidine hydrochloride, mass fraction 0.5%, and reaction temperature is
55 DEG C, reaction time 12h.
Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two are 1 in mass ratio:4 mix in water, room temperature
12h is reacted, obtains long-chain branch amphipathic polymer.
It is 3 by volume:10, be by emulsifier aqueous solution and viscosity that long-chain branch amphipathic polymer concentration is 2.0mg/mL
1300mPa.s viscous crude mixing, 50 DEG C of stirrings form emulsified viscous oil liquid.
Embodiment 5
The preparation of terpolymer containing epoxy radicals：By acrylamide 2.886g, 2- acrylamido -2- methyl-prop sulphurs
Sour 2.107g, GMA 0.008mL, which are dissolved in 45mL dimethyl sulfoxide (DMSO)s, carries out free radicals copolymerization reaction,
Acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, the molfraction ratio of GMA are 79.9:20:
0.1, monomer mass fraction is 10%.Initiator is azodiisobutyronitrile 0.025g, mass fraction 0.5%, and reaction temperature is
65 DEG C, reaction time 10h.
The preparation of the membered copolymer of Amino End Group two：By acrylamide 5.796g, SSS 4.205g, mercaptoethylmaine
0.050g, which is dissolved in 50mL water, carries out free radicals copolymerization reaction, and acrylamide, the molfraction ratio of SSS are 80:
20, monomer mass fraction is 20%.Initiator is azo diisobutyl amidine hydrochloride, mass fraction 0.5%, and reaction temperature is
55 DEG C, reaction time 12h.
Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two are 1 in mass ratio:3 mix in water, room temperature
12h is reacted, obtains long-chain branch amphipathic polymer.
It is 3 by volume:7, be by emulsifier aqueous solution and viscosity that long-chain branch amphipathic polymer concentration is 2.0mg/mL
1300mPa.s viscous crude mixing, 50 DEG C of stirrings form emulsified viscous oil liquid.
Embodiment 6
The preparation of terpolymer containing epoxy radicals：By acrylamide 2.835g, 2- acrylamido -2- methyl-prop sulphurs
Sour 2.095g, GMA 0.070mL, which are dissolved in 45mL dimethyl sulfoxide (DMSO)s, carries out free radicals copolymerization reaction,
Acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, the molfraction ratio of GMA are 79.0:20:
1.0, monomer mass fraction is 10%.Initiator is azodiisobutyronitrile 0.025g, mass fraction 0.5%, and reaction temperature is
65 DEG C, reaction time 10h.
The preparation of the membered copolymer of Amino End Group two：By acrylamide 5.796g, SSS 4.204g, mercaptoethylmaine
0.050g, which is dissolved in 50mL water, carries out free radicals copolymerization reaction, and acrylamide, the molfraction ratio of SSS are 80:
20, monomer mass fraction is 20%.Initiator is azo diisobutyl amidine hydrochloride, mass fraction 0.5%, and reaction temperature is
55 DEG C, reaction time 12h.
Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two are 1 in mass ratio:2 mix in water, room temperature
12h is reacted, obtains long-chain branch amphipathic polymer.
It is 3 by volume:7, be by emulsifier aqueous solution and viscosity that long-chain branch amphipathic polymer concentration is 5.0mg/mL
1300mPa.s viscous crude mixing, 40 DEG C of stirrings form emulsified viscous oil liquid.
Embodiment 7
The preparation of terpolymer containing epoxy radicals：By acrylamide 2.835g, 2- acrylamido -2- methyl-prop sulphurs
Sour 2.095g, GMA 0.069mL, which are dissolved in 45mL dimethyl sulfoxide (DMSO)s, carries out free radicals copolymerization reaction,
Acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, the molfraction ratio of GMA are 79.0:20:
1.0, monomer mass fraction is 10%.Initiator is azodiisobutyronitrile 0.025g, mass fraction 0.5%, and reaction temperature is
65 DEG C, reaction time 10h.
The preparation of the membered copolymer of Amino End Group two：By acrylamide 5.795g, SSS 4.204g, mercaptoethylmaine
0.050g, which is dissolved in 50mL water, carries out free radicals copolymerization reaction, and acrylamide, the molfraction ratio of SSS are 80:
20, monomer mass fraction is 20%.Initiator is azo diisobutyl amidine hydrochloride, mass fraction 0.5%, and reaction temperature is
55 DEG C, reaction time 12h.
Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two are 1 in mass ratio:5 mix in water, room temperature
12h is reacted, obtains long-chain branch amphipathic polymer.
It is 3 by volume:7, be by emulsifier aqueous solution and viscosity that long-chain branch amphipathic polymer concentration is 1.5mg/mL
1300mPa.s viscous crude mixing, 50 DEG C of stirrings form emulsified viscous oil liquid.
Embodiment 8
The preparation of terpolymer containing epoxy radicals：By acrylamide 2.835g, 2- acrylamido -2- methyl-prop sulphurs
Sour 2.093g, GMA 0.070mL, which are dissolved in 45mL dimethyl sulfoxide (DMSO)s, carries out free radicals copolymerization reaction,
Acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, the molfraction ratio of GMA are 79.0:20:
1.0, monomer mass fraction is 10%.Initiator is azodiisobutyronitrile 0.025g, mass fraction 0.5%, and reaction temperature is
65 DEG C, reaction time 10h.
The preparation of the membered copolymer of Amino End Group two：By acrylamide 5.796g, SSS 4.204g, mercaptoethylmaine
0.050g, which is dissolved in 50mL water, carries out free radicals copolymerization reaction, and acrylamide, the molfraction ratio of SSS are 80:
20, monomer mass fraction is 20%.Initiator is azo diisobutyl amidine hydrochloride, mass fraction 0.5%, and reaction temperature is
55 DEG C, reaction time 12h.
Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two are 1 in mass ratio:5 mix in water, room temperature
12h is reacted, obtains long-chain branch amphipathic polymer.
It is 3 by volume:7, be by emulsifier aqueous solution and viscosity that long-chain branch amphipathic polymer concentration is 1.0mg/mL
1300mPa.s viscous crude mixing, 60 DEG C of stirrings form emulsified viscous oil liquid.
Embodiment 9
The preparation of terpolymer containing epoxy radicals：By acrylamide 2.835g, 2- acrylamido -2- methyl-prop sulphurs
Sour 2.093g, GMA 0.070mL, which are dissolved in 45mL dimethyl sulfoxide (DMSO)s, carries out free radicals copolymerization reaction,
Acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, the molfraction ratio of GMA are 79.0:20:
1.0, monomer mass fraction is 10%.Initiator is azodiisobutyronitrile 0.025g, mass fraction 0.5%, and reaction temperature is
65 DEG C, reaction time 10h.
The preparation of the membered copolymer of Amino End Group two：By acrylamide 5.795g, SSS 4.204g, mercaptoethylmaine
0.050g, which is dissolved in 50mL water, carries out free radicals copolymerization reaction, and acrylamide, the molfraction ratio of SSS are 80:
20, monomer mass fraction is 20%.Initiator is azo diisobutyl amidine hydrochloride, mass fraction 0.5%, and reaction temperature is
55 DEG C, reaction time 12h.
Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two are 1 in mass ratio:5 mix in water, room temperature
12h is reacted, obtains long-chain branch amphipathic polymer.
It is 3 by volume:7, be by emulsifier aqueous solution and viscosity that long-chain branch amphipathic polymer concentration is 0.5mg/mL
1300mPa.s viscous crude mixing, 50 DEG C of stirrings form emulsified viscous oil liquid.
Comparative example 1
As described in Example 1, unlike：The terpolymer of epoxy radicals will be contained as emulsifying agent.
Comparative example 2
As described in Example 1, unlike：Using the membered copolymer of Amino End Group two as emulsifying agent.
Comparative example 3
As described in Example 1, unlike：Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two press quality
Than for 1:1 mixes in water, reacts at room temperature 12h, obtains long-chain branch amphipathic polymer, two membered copolymers are very few to thick oil emulsifier
Emulsifiability is poor.
Comparative example 4
As described in Example 1, unlike：Terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two press quality
Than for 1:10 mix in water, react at room temperature 12h, obtain long-chain branch amphipathic polymer, two membered copolymers are excessively to emulsified viscous oil
Performance is equally poor.
Test example 1
Embodiment 1 and comparative example 1-4 amphipathic polymer are subjected to emulsifiability test, emulsifier concentration identical condition
Under each example emulsification situation it is as shown in table 1.Understand, the emulsifiability of embodiment 1 is more excellent, and the emulsifiability of comparative example 1,2 is worst, right
The performance of ratio 3,4 is general.
The comparison of the aqueous solution emulsifiability of table 1.
Test example 2
Embodiment 1 and comparative example 1-4 amphipathic polymer are subjected to anti-salt property test
By the emulsifying agent of embodiment 1 and comparative example 1-4 be configured to various concentrations the aqueous solution and 0.1mol/L NaCl it is molten
Liquid, carry out the test of surface tension at room temperature and compare.
For the emulsifying agent of embodiment 1 under various concentrations, no matter can show in water or in 0.1mol/L NaCl solutions
Writing reduces the surface tension of water, and the surface tension of 0.1mol/L NaCl solutions is significantly lower than the surface tension of the aqueous solution, such as breast
When agent concentration is 2.0mg/mL, 0.1mol/L NaCl solutions surface tension is 32.07mN/m, and the surface tension of the aqueous solution
For 37.41mN/m.Illustrate that the emulsifying agent of embodiment 1 has good salt resistant character.
, no matter can one in water or in 0.1mol/L NaCl solutions for the emulsifying agent of comparative example 1 under various concentrations
Reduce the surface tension of water with determining degree, and the surface tension of 0.1mol/L NaCl solutions is less than the surface tension of the aqueous solution, such as
When emulsifier concentration is 2.0mg/mL, 0.1mol/L NaCl solutions surface tension is 55.42mN/m, and the surface of the aqueous solution
Power is 57.59mN/m.Illustrate that the emulsifying agent of comparative example 1 has certain surface-active and salt tolerance, but much not as good as the breast of embodiment 1
Agent.
For the emulsifying agent of comparative example 2 under various concentrations, the surface tension of its aqueous solution is larger, and 0.1mol/L
The surface tension of NaCl solution is then much smaller, if the surface tension of the 2.0mg/mL aqueous solution is 68.09mN/m, with concentration
The surface tension of 0.1mol/L NaCl solutions is 45.09mN/m.Illustrate the emulsifying agent of comparative example 2 surface-active under the conditions of saliferous
It is stronger.
, no matter can one in water or in 0.1mol/L NaCl solutions for the emulsifying agent of comparative example 3 under various concentrations
Reduce the surface tension of water with determining degree, and the surface tension of 0.1mol/L NaCl solutions is less than the surface tension of the aqueous solution, such as
When emulsifier concentration is 2.0mg/mL, 0.1mol/L NaCl solutions surface tension is 46.84mN/m, and the surface of the aqueous solution
Power is 48.84mN/m.Illustrating the emulsifying agent of comparative example 3 has certain a surface-active and salt tolerance, but compared with embodiment 1 still suffer from compared with
Big gap.
For the emulsifying agent of comparative example 4 under various concentrations, no matter can be dropped in water or in 0.1mol/L NaCl solutions
The surface tension of low water, and the surface tension of 0.1mol/L NaCl solutions is slightly below the surface tension of the aqueous solution, as emulsifying agent is dense
Spend for 2.0mg/mL when, 0.1mol/L NaCl solutions surface tension is 48.37mN/m, and the surface tension of the aqueous solution is
49.38mN/m.Illustrate that the emulsifying agent of comparative example 4 has certain salt resistant character, but much not as good as the emulsifying agent of embodiment 1.
Test example 3
Embodiment 1 and comparative example 1-4 emulsifying agent are subjected to heat resistance test
The emulsifying agent of embodiment 1 and comparative example 1-4 is configured to the aqueous solution of various concentrations, carries out the alternating temperature of surface tension
Test and compare.
For the emulsifier aqueous solution of embodiment 1 under various concentrations, its surface tension is raised and reduced with temperature, when molten
When liquid concentration is 2.0mg/mL, 60 DEG C of lower surface tension force can as little as 31.22mN/m, show good temperature tolerance.For difference
The emulsifier aqueous solution of comparative example 1 under concentration, its surface tension slightly reduces with temperature rise, when solution concentration is 2.0mg/
During mL, 60 DEG C of lower surface tension force can as little as 55.07mN/m, show certain temperature tolerance.For the comparative example 2 under various concentrations
Emulsifier aqueous solution, its surface tension raise obvious reduction, when solution concentration is 2.0mg/mL, 60 DEG C of lower surfaces with temperature
Tension force is down to 55.39mN/m, and its surface-active has good temperature tolerance.For the emulsifying agent water of comparative example 3 under various concentrations
Solution, its surface tension slightly reduce with temperature rise, and when solution concentration is 2.0mg/mL, 60 DEG C of lower surface tension force can be low
To 42.78mN/m, certain temperature tolerance is shown.For the emulsifier aqueous solution of comparative example 4 under various concentrations, its surface tension
Raise and reduce with temperature, when solution concentration is 2.0mg/mL, 60 DEG C of lower surface tension force can as little as 46.95mN/m, also table
Reveal certain temperature tolerance.To sum up, the heat resistance of the emulsifying agent of embodiment 1 is more preferable under the same terms, while production cost is low, production
Go out efficiency high.
Claims (10)
1. a kind of preparation method of long-chain branch amphipathic polymer, including：
The hybrid reaction in water by the terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two；
The mass ratio of terpolymer containing epoxy radicals and the membered copolymer of Amino End Group two is 1:2~1:5, the reaction time be 10~
15h；
The terpolymer containing epoxy radicals is by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, methacrylic acid
Ethylene oxidic ester copolyreaction is made；
The membered copolymer of Amino End Group two is copolymerized by acrylamide, SSS, mercaptoethylmaine and is made.
2. the preparation method of amphipathic polymer according to claim 1, it is characterised in that the ternary containing epoxy radicals
In the copolyreaction of copolymer, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, GMA
Molfraction ratio is (79.0~79.9)：20：(1.0~0.1).
3. the preparation method of amphipathic polymer according to claim 1, it is characterised in that the ternary containing epoxy radicals
In the copolyreaction of copolymer, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and GMA
The mass fraction that monomer populations account for reaction system is 10~20%.
4. the preparation method of amphipathic polymer according to claim 1, it is characterised in that the ternary containing epoxy radicals
The copolyreaction of copolymer is reacted under initiator initiation, and initiator is azodiisobutyronitrile, and initiator accounts for reaction system
Mass fraction be 0.1~0.5%.
5. the preparation method of amphipathic polymer according to claim 1, it is characterised in that the ternary containing epoxy radicals
The copolyreaction temperature of copolymer is 60~70 DEG C.
6. the preparation method of amphipathic polymer according to claim 1, it is characterised in that the ternary containing epoxy radicals
The copolyreaction time of copolymer is 6~15h.
7. the preparation method of amphipathic polymer according to claim 1, it is characterised in that the membered copolymer of Amino End Group two
Copolyreaction in, acrylamide, the molfraction ratio of SSS are (90.0~50.0):(10.0~50.0)；
Preferably, the quality of mercaptoethylmaine accounts for the 0.3~1% of acrylamide and SSS gross mass.
8. the preparation method of amphipathic polymer according to claim 1, it is characterised in that the membered copolymer of Amino End Group two
Copolyreaction in, the mass fraction that the monomer populations of acrylamide and SSS account for reaction system is 15~25%.
9. the preparation method of an amphipathic polymer according to claim 1, it is characterised in that the Amino End Group two-spot copolymerization
In the copolyreaction of thing, reacted under initiator initiation, initiator is azo diisobutyl amidine hydrochloride, and initiator accounts for instead
The mass fraction for answering system is 0.5~1.0%.
10. the preparation method of an amphipathic polymer according to claim 1, it is characterised in that the Amino End Group two-spot is total to
In the copolyreaction of polymers, copolyreaction temperature is 50~60 DEG C, and the combined polymerization time is 10~15h.
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