CN106279711A - A kind of preparation method of environmentally friendly macromole emulsifying agent - Google Patents
A kind of preparation method of environmentally friendly macromole emulsifying agent Download PDFInfo
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- CN106279711A CN106279711A CN201610653682.5A CN201610653682A CN106279711A CN 106279711 A CN106279711 A CN 106279711A CN 201610653682 A CN201610653682 A CN 201610653682A CN 106279711 A CN106279711 A CN 106279711A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
The present invention relates to the preparation method of a kind of environmentally friendly macromole emulsifying agent, use controlled activity polymerizating technology (ATRP, SET LRP) the design potential hydrophilic segment of complex functionality and hydrophobic segment, then by Diels Alder reaction, potential hydrophilic segment and hydrophobic segment are linked together, amphipathic nature block polymer is i.e. can get after hydrolyzed under acidic conditions, this amphipathic nature block polymer can be self-assembly of micelle in water, hydrophilic segment and the hydrophobic segment fracture of this micelle can be made under ultrasonic force effect, there occurs Diels Alder back reaction.The end group discharged after ultrasonic fracture is that the hydrophilic segment of anthracene has fluorescent effect, can be detected by fluorescence spectrophotometer.This macromole emulsifying agent can be used for preparing functional latex particle, additionally, due to this macromole emulsifying agent is amphipathic nature block polymer and the sensitivity to ultrasonic force, it has the application that some are potential in biomedicine.
Description
Technical field
The invention belongs to the preparation method of emulsifying agent, be specifically related to the preparation side of a kind of environmentally friendly macromole emulsifying agent
Method.
Background technology
At present, emulsion polymerization remains a kind of application technology preparing latex widely, such as rubber latex, pressure-sensitive
Glue, emulsion paint, functional coat and coating and some functional brush particles etc..It is different from polymerisation in bulk and polymerisation in solution,
Emulsion is polymerized with water as medium, and heat radiation is good, and reaction temperature is controlled, and reaction rate is high, can obtain the polymer of high molecular,
Thus it is widely used in industrial quarters and academia already.But, emulsion polymerization process needs to use emulsifying agent, substantial amounts of little molecule
Emulsifying agent brings difficulty to follow-up removing emulsifying agent process, and additionally in application process, the migration of emulsifying agent can affect the entirety of material
Performance, being directly discharged in the natural water such as river, ocean of substantial amounts of small-molecular emulsifier, water pollution can be caused, consume
Dissolved oxygen in water, endangers aquatile, causes the deterioration of the ecological environment.Therefore, a kind of environmentally friendly recyclable profit again of exploitation
Macromole emulsifying agent be particularly important.
Summary of the invention
Solve the technical problem that
In place of the deficiencies in the prior art, the present invention proposes the preparation of a kind of environmentally friendly macromole emulsifying agent
Method, uses controlled activity polymerizating technology, utilizes the reversibility that Diels Alder reacts, and design synthesis is a kind of environmentally friendly
Can the macromole emulsifying agent of ultrasonic fracture.
Technical scheme
The preparation method of a kind of environmentally friendly macromole emulsifying agent, it is characterised in that step is as follows:
Step 1: 8～10 parts of monomer A of addition in equipped with the reaction tube of magneton, ligand 1～3 parts, cuprous bromide 1～3 parts,
Functional anthracene initiator 0.05～0.1 part, solvent 8～10 parts, after the oxygen in three freeze-thaw cycle removal systems and water,
Reacting 5～10h under inert gas shielding under room temperature, reaction obtains end group anthracene functionalized polymer after terminating to purify；
8～10 parts of monomer B, ligand 1～3 parts, functionalization maleic anhydride initiator is added in equipped with the reaction tube of magneton
0.05～0.1 part, copper bromide 1～3 parts, solvent 8～10 parts, after oxygen in three freeze-thaw cycle removal systems and water, add
Entering 0.5cm～the 1cm copper cash processed, room temperature reaction 5～10h under inert gas shielding, reaction obtains end group after terminating to purify
The polymer of maleic anhydride functional；
Step 2: add end group anthracene functionalized polymer 5～8 parts, end group maleic anhydride merit in equipped with the reaction tube of magneton
The polymer 8 of energyization～10 parts, toluene 8～10 parts, in logical nitrogen 1h removal system after oxygen, reactor is placed in 120 DEG C of oil
Reacting 48h in bath, reaction obtains di-block copolymer after terminating purification processes；
Step 3: add di-block copolymer 8～10 parts in equipped with the reaction tube of magneton, dichloromethane 40～50 parts, three
Fluoroethanoic acid 8～10 parts, react 48h under room temperature, reaction obtains amphipathic nature block polymer after terminating purification processes；
Step 4: add amphipathic inlay and break copolymer 5～10 parts in equipped with the single port bottle of magneton, sodium hydroxide 4～8 parts,
Water 40～50 parts, stir the 2～3h micellar solution i.e. environmental friendliness obtaining as clear as crystal amphipathic inlay and break copolymer at 80 DEG C
Type macromole emulsifying agent.
Described monomer A is the one of Tert-butyl Methacrylate, tert-butyl acrylate or NIPA or many
Kind.
Described monomer B is one or more in n-butyl acrylate, n-BMA or styrene.
Described part is three (2-dimethylaminoethyl) amine, pentamethyl-diethylenetriamine, 4,4 '-dinonyl-2,2 '-connection pyrrole
One or more in pyridine.
Described solvent is one or more in dimethyl sulfoxide, toluene, dimethylformamide.
The good solvent that in described step, purification process is used is oxolane, and poor solvent is methanol, hexamethylene.
Beneficial effect
The preparation method of a kind of environmentally friendly macromole emulsifying agent that the present invention proposes, uses controlled activity polymerizating technology
(ATRP, SET-LRP) design potential hydrophilic segment of complex functionality and hydrophobic segment, then will by Diels Alder reaction
Potential hydrophilic segment and hydrophobic segment link together, and i.e. can get amphipathic nature block polymer after hydrolyzed under acidic conditions, should
Amphipathic nature block polymer can be self-assembly of micelle in water, can make the hydrophilic segment of this micelle and hydrophobic under ultrasonic force effect
Segment ruptures, and there occurs Diels Alder back reaction.The end group discharged after ultrasonic fracture is that the hydrophilic segment of anthracene has fluorescence
Effect, can be detected by fluorescence spectrophotometer.
This macromole emulsifying agent can be used for preparing functional latex particle, additionally, due to this macromole emulsifying agent is amphiphilic
Property block copolymer and the sensitivity to ultrasonic force, it has the application that some are potential in biomedicine.
Present invention have the advantage that
1, use controlled activity polymerizating technology (ATRP, SET-LRP), the length of hydrophilic segment and hydrophobic segment can be precisely controlled
Short, control polymerization used is simple to operate, and reaction condition is gentle, can carry out under room temperature.
2, the amphipathic nature block polymer of design synthesis can be used for making as a kind of environmentally friendly macromole emulsifying agent
Standby functional latex particle, can realize breakdown of emulsion, and recyclable recycling under ultrasonic force effect, it addition, this amphipathic block is altogether
Polymers has potential application in biomedicine.
Accompanying drawing explanation
Fig. 1: amphipathic nature block polymer schematic diagram
Fluorescence spectrum figure (emission spectrum: λ after Fig. 2: PBA-b-PAA micellar solution is ultrasonicexc=260nm, excitation spectrum:
λem=420nm)
Detailed description of the invention
In conjunction with embodiment, accompanying drawing, the invention will be further described:
Embodiment 1: the preparation of a kind of environmentally friendly macromole emulsifying agent
Tert-butyl Methacrylate 8 parts, part three (2-dimethylaminoethyl) amine 1 is added in equipped with the reaction tube of magneton
Part, cuprous bromide 1 part, functional anthracene initiator 0.05 part, dimethyl sulfoxide 8 parts, in three freeze-thaw cycle removal systems
Oxygen and water after, react 7h under inert gas shielding under room temperature, reaction obtains the poly-first of end group anthracene functionalization after terminating to purify
Base tert-butyl acrylate long-chain-segment；
Butyl methacrylate 8 parts, part pentamethyl-diethylenetriamine 1 part, merit is added in equipped with the reaction tube of magneton
Can change maleic anhydride initiator 0.05 part, copper bromide 1 part, dimethylformamide 8 parts, in three freeze-thaw cycle removal systems
After oxygen and water, the 0.5cm copper cash that addition processed, room temperature reaction 8h under inert gas shielding, reaction obtains after terminating to purify
The Vinalac 5920 long-chain-segment of end group maleic anhydride functional；
5 parts of the polymethyl tert-butyl acrylate polymer of above-mentioned anthracene functionalization, horse is added in equipped with the reaction tube of magneton
Come 8 parts of the Vinalac 5920 polymer of Anhydride functional, toluene 8 parts, lead in nitrogen 1h removal system after oxygen, will
Reactor is as reacting 48h in 120 DEG C of oil baths, it is polymethyl tert-butyl acrylate that reaction obtains one end after terminating purification processes,
One end is the di-block copolymer of Vinalac 5920；
Above-mentioned block copolymer 8 parts, dichloromethane 40 parts, trifluoroacetic acid 8 parts, room is added in equipped with the reaction tube of magneton
Reacting 48h under temperature, it is polymethylacrylic acid that reaction obtains one end after terminating purification processes, and one end is Vinalac 5920
The most environmentally friendly macromole emulsifying agent of amphipathic nature block polymer.
Embodiment 2: the preparation of a kind of environmentally friendly macromole emulsifying agent
Tert-butyl acrylate 8 parts, part pentamethyl-diethylenetriamine 2 parts, bromination is added in equipped with the reaction tube of magneton
Cuprous 1 part, functional anthracene initiator 0.05 part, dimethyl sulfoxide 8 parts, the oxygen in three freeze-thaw cycle removal systems and
After water, reacting 5h under inert gas shielding under room temperature, reaction obtains the tertiary fourth of polyacrylic acid of end group anthracene functionalization after terminating to purify
Ester long-chain-segment；
Butyl acrylate 8 parts, part pentamethyl-diethylenetriamine 2 parts, functionalization is added in equipped with the reaction tube of magneton
Maleic anhydride initiator 0.05 part, copper bromide 1 part, dimethylformamide 8 parts, oxygen in three freeze-thaw cycle removal systems
After water, the 0.5cm copper cash that addition processed, room temperature reaction 6h under inert gas shielding, reaction obtains end group after terminating to purify
The polyacrylic acid N-butyl long-chain-segment of maleic anhydride functional；
5 parts of the polyacrylic acid tert-butyl ester polymer of above-mentioned anthracene functionalization, maleic acid is added in equipped with the reaction tube of magneton
8 parts of the polyacrylic acid N-butyl polymer of anhydride functional, toluene 8 parts, in logical nitrogen 1h removal system after oxygen, by reactor extremely
Reacting 48h in 120 DEG C of oil baths, it is the polyacrylic acid tert-butyl ester that reaction obtains one end after terminating purification processes, and one end is polypropylene
The di-block copolymer of acid N-butyl；
Above-mentioned block copolymer 10 parts is added in equipped with the reaction tube of magneton, dichloromethane 50 parts, trifluoroacetic acid 8 parts,
Reacting 48h under room temperature, it is polyacrylic acid that reaction obtains one end after terminating purification processes, and one end is the amphiphilic of polyacrylic acid N-butyl
The property the most environmentally friendly macromole emulsifying agent of block copolymer.
Embodiment 3: the preparation of a kind of environmentally friendly macromole emulsifying agent
Tert-butyl acrylate 8 parts, part 4,4 '-dinonyl-2,2 '-bipyridyl 2 is added in equipped with the reaction tube of magneton
Part, cuprous bromide 1 part, functional anthracene initiator 0.1 part, dimethylformamide 8 parts, in three freeze cycle removal systems
Oxygen and water after, under inert gas shielding under room temperature react 10h, reaction terminate purify after obtain poly-the third of end group anthracene functionalization
Enoic acid ter-butyl ester long-chain-segment；
Styrene 8 parts, part three (2-dimethylaminoethyl) amine 2 parts, functionalization is added in equipped with the reaction tube of magneton
Maleic anhydride initiator 0.1 part, copper bromide 1 part, toluene 8 parts, after oxygen in three freeze cycle removal systems and water, add
Entering the 1cm copper cash processed, room temperature reaction 10h under inert gas shielding, reaction obtains end group maleic anhydride merit after terminating to purify
The polystyrene long-chain-segment of energyization；
Polyacrylic acid tert-butyl ester polymer part of above-mentioned anthracene functionalization, maleic anhydride is added in equipped with the reaction tube of magneton
The poly styrene polymer of functionalization 8 parts, toluene 8 parts, in logical nitrogen 1h removal system after oxygen, by reactor as 120 DEG C
Reacting 48h in oil bath, it is the polyacrylic acid tert-butyl ester that reaction terminates to obtain one end after purification processes, and one end is the two embedding of polystyrene
Section copolymer；
Above-mentioned block copolymer 10 parts is added in equipped with the reaction tube of magneton, dichloromethane 50 parts, trifluoroacetic acid 10 parts,
Reacting 48h under room temperature, it is polyacrylic acid that reaction obtains one end after terminating purification processes, and one end is the amphipathic block of polystyrene
The most environmentally friendly macromole emulsifying agent of copolymer.
Visible, this preparation method uses controlled activity polymerizating technology (ATRP, SET-LRP) to be prepared for the latent of end group functional
At hydrophilic segment segment and hydrophobic segment, then utilizing Diels Alder reaction to obtain one end is potential hydrophilic segment, one end
For the di-block copolymer of hydrophobic segment, the tert-butyl group that hydrolyzed under acidic conditions is removed in above-mentioned block copolymer has just obtained two
Parent's property block copolymer, this amphipathic nature block polymer can be self-assembly of micelle in water, can make this glue under ultrasonic force effect
The hydrophilic segment of bundle and hydrophobic segment fracture, there occurs Diels Alder back reaction, and this amphipathic nature block polymer can be as greatly
Molecule emulsifying agent, prepares functional latex particle.Amphipathic nature block polymer prepared by the present invention can be as a kind of environmental protection
Type macromole emulsifying agent, provides new thinking for the problem removing emulsifying agent difficult in commercial production, and according to Diels Alder
The reversibility of reaction, after the ultrasonic fracture of amphipathic nature block polymer in the present invention, hydrophobic segment part is tangled in polymer beads
Son is internal, it is difficult to migrate, and hydrophilic chain segment part can be directly dissolved in water, can with recycling, thus can reach energy-conservation
The purpose reduced discharging.
Claims (6)
1. the preparation method of an environmentally friendly macromole emulsifying agent, it is characterised in that step is as follows:
Step 1: add 8～10 parts of monomer A, ligand 1～3 parts, cuprous bromide 1～3 parts, function in equipped with the reaction tube of magneton
Property anthracene initiator 0.05～0.1 part, solvent 8～10 parts, after the oxygen in three freeze-thaw cycle removal systems and water, inertia
Reacting 5～10h under gas shield under room temperature, reaction obtains end group anthracene functionalized polymer after terminating to purify；
8～10 parts of monomer B, ligand 1～3 parts, functionalization maleic anhydride initiator 0.05 is added in equipped with the reaction tube of magneton
～0.1 part, copper bromide 1～3 parts, solvent 8～10 parts, after oxygen in three freeze-thaw cycle removal systems and water, at addition
0.5cm～the 1cm copper cash managed, room temperature reaction 5～10h under inert gas shielding, reaction obtains end group Malaysia after terminating to purify
The polymer of Anhydride functional；
Step 2: add end group anthracene functionalized polymer 5～8 parts, end group maleic anhydride functional in equipped with the reaction tube of magneton
Polymer 8～10 parts, toluene 8～10 parts, in logical nitrogen 1h removal system after oxygen, reactor is placed in 120 DEG C of oil baths
Reaction 48h, reaction obtains di-block copolymer after terminating purification processes；
Step 3: add di-block copolymer 8～10 parts, dichloromethane 40～50 parts, trifluoro second in equipped with the reaction tube of magneton
Acid 8～10 parts, reacts 48h under room temperature, reaction obtains amphipathic nature block polymer after terminating purification processes；
Step 4: add amphipathic inlay and break copolymer 5～10 parts, sodium hydroxide 4～8 parts, water 40 in equipped with the single port bottle of magneton
～50 parts, stirring 2～3h at 80 DEG C, to obtain the micellar solution of as clear as crystal amphipathic inlay and break copolymer the most environmentally friendly greatly
Molecule emulsifying agent.
The preparation method of the most environmentally friendly macromole emulsifying agent, it is characterised in that: described monomer A
For Tert-butyl Methacrylate, one or more of tert-butyl acrylate or NIPA.
The preparation method of the most environmentally friendly macromole emulsifying agent, it is characterised in that: described monomer B
For one or more in n-butyl acrylate, n-BMA or styrene.
The preparation method of the most environmentally friendly macromole emulsifying agent, it is characterised in that: described part is
Three (2-dimethylaminoethyl) amine, pentamethyl-diethylenetriamine, 4,4 '-dinonyl-2,2 ' one or more in-bipyridyl.
The preparation method of the most environmentally friendly macromole emulsifying agent, it is characterised in that: described solvent is
One or more in dimethyl sulfoxide, toluene, dimethylformamide.
The preparation method of the most environmentally friendly macromole emulsifying agent, it is characterised in that: in described step
The good solvent that purification process is used is oxolane, and poor solvent is methanol, hexamethylene.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768283A (en) * | 2019-01-16 | 2019-05-17 | 惠州亿纬锂能股份有限公司 | A kind of silicon-based anode binder and preparation method thereof |
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2016
- 2016-08-10 CN CN201610653682.5A patent/CN106279711A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| HUI LI: "Promoting Mechanochemistry of Covalent Bonds by Noncovalent Micellar Aggregation", 《ACS MACRO LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768283A (en) * | 2019-01-16 | 2019-05-17 | 惠州亿纬锂能股份有限公司 | A kind of silicon-based anode binder and preparation method thereof |
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