CN103012638A - Method for synthesizing high solid content polymer microemulsion - Google Patents
Method for synthesizing high solid content polymer microemulsion Download PDFInfo
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Abstract
The invention belongs to the field of microemulsion polymerization, and particularly relates to a novel technology for synthesizing high solid content polymer microemulsion. The novel technology comprises the following steps of: firstly, carrying out copolymerization on a silicon monomer and an ethylene monomer by a free radical polymerization method so as to form copolymer; and then adding the copolymer serving as an emulsifier/co-emulsifier into initiation solution and slowly and dropwise adding an acrylic acid monomer into an initiation system in a total differential feeding manner so as to form acrylic acid emulsion. The microemulsion prepared by the novel technology has the advantages of small particle size, low viscosity, narrow particle size distribution, high polymerization efficiency, no volatility and solid content of 50 weight percent; and polymer particles can comprise various functional groups such as amido, hydroxy, carboxyl and the like. Moreover, the preparation process is simple and is easy to control. The microemulsion prepared by the novel technology can be widely used for encapsulation, an innovative and high technical coating, a catalyst carrier and a waveguide material and the like.
Description
Technical field
The invention belongs to the micro-emulsion polymerization field, is a kind of synthetic technology of novel high-solid content polymer microemulsion.
Background technology
Microemulsion (Microemulsion Polymerization) is transparent and homogeneous or the translucent thermodynamically stable colloidal dispersion system of immiscible oil and water and an amount of spontaneous formation of emulsifying agent (or emulsifying agent/assistant for emulsifying agent).1980, Stoff and Bone studied the polymerization behavior of methyl acrylate in SDS/ amylalcohol/methyl acrylate/water microemulsion first, thereby had caused the research of people to polyreaction in the Microemulsion, had opened up the frontier of letex polymerization.There are significant difference in micro-emulsion polymerization and letex polymerization, micro-emulsion polymerization can prepare the latex of transparent and stable, polymer particle especially little (10-100nm), specific surface area is large especially, has many potential application in fields such as coating, catalysis and drug release.Yet, two important drawbacks limit the application of microemulsion polymerization method: (1) emulsifier content is high, and massfraction is greater than 10% usually.Monomer/emulsifying agent ratio is then less than 1; (2) polymer content of microemulsion is lower, and massfraction is less than 10% usually.
In order to overcome two large shortcomings of microemulsion, researchist both domestic and external has carried out effectively working, they are by changing polymerization technique and using new and effective emulsifying agent, the consumption that obtains Microemulsion Emulsifier accounts for the system total amount and is down to 1-2%, the polymkeric substance particle diameter is down to below the 30nm, the advantages such as polymkeric substance particle diameter narrow distribution.Generally speaking, there are many problems to need to solve on above researchist's the achievement.These problems comprise: need add assistant for emulsifying agent, must use higher emulsifying agent/monomer ratio and lower monomers/water ratio, and the solid content of gained microemulsion is relatively not high, these have restricted the industrial applications of micro-emulsion polymerization technology.
Summary of the invention
The object of the invention is to propose a kind of synthetic method of novel high-solid content polymer microemulsion.
The synthetic method of the novel high-solid content polymer microemulsion that the present invention proposes may further comprise the steps:
(1) with silicon-containing monomer and vinyl monomer copolymerization multipolymer as emulsifying agent/assistant for emulsifying agent;
(2) with the water-soluble water that becomes of emulsifying agent;
(3) emulsifying agent/assistant for emulsifying agent synthetic in (1) is dissolved in monomer and is mixed into oil phase;
(4) in aqueous phase solution, add initiator, slowly drip continuously the oil-phase solution polymerization and get the microemulsion product.
Specifically can be:
(1) silicon-containing monomer and vinyl monomer are used the active free radical polymerization method synthetic copolymer;
The emulsifiers dissolve that (2) will account for total amount 1-3% becomes water in the deionized water that accounts for total amount 50-90%;
(3) will account for total amount 1-3% multipolymer emulsifying agent/assistant for emulsifying agent is dissolved in and accounts for one kind of total amount 10-50% or more than one monomers are mixed into oil phase;
(4) water is added be connected in the four-hole boiling flask of prolong and agitator, add and account for total amount 0.1-0.5% initiator, logical nitrogen is also kept 72 ℃, and oil phase slowly is added dropwise to polymerization 5-6h in the reaction system continuously, naturally cools to discharging after the room temperature.
The present invention more specifically step is as follows:
1, use the free radical polymerisation process synthetic copolymer:
(1) preparation of macromole evocating agent:
Monomer, initiator, catalyzer, part and solvent are added in the reaction vessel, be filled with nitrogen or argon gas after reaction system vacuumized repeatedly, at 90-120 ℃, react 6-15h under the magnetic agitation, final product desolventizing and catalyzer obtain macromole evocating agent.
(2) preparation of silicon-containing monomer and vinyl monomer multipolymer:
Macromole evocating agent with (1) preparation, catalyzer, part, silicon-containing monomer and solvent add reaction vessel, after vacuumizing repeatedly, reaction system is filled with nitrogen or argon gas, lower cause the silicon-containing monomer polymerization at 105-110 ℃, final product desolventizing and catalyzer are prepared the multipolymer of silicon-containing monomer and vinyl monomer.
2, the emulsifying agent of total amount 1-3%, emulsifying agent/assistant for emulsifying agent and the deionized water of total amount 1-3% are mixed with solution, form transparent aqueous phase solution.The more excellent consumption of the emulsifying agent here is the 2-3% of total amount.The consumption of deionized water is the 50-90% of total amount.
3, accurately weighing to account for the monomer composition oil-phase solution of total amount 10-50% for subsequent use.
4, in the four-hole boiling flask that is connected to prolong and agitator, add the initiator that accounts for total amount 0.1-0.5%, to be warming up to by the aqueous phase solution that step 2 makes 65 ℃ of decomposition of initiator temperature, logical nitrogen in system, deoxygenation, the oil-phase solution that step 3 is made adds in the reaction system in differential mode (slowly continuously), keeps nitrogen atmosphere, is warming up to 72 ℃, stirring at low speed, 3-4h drips off.Slowly dripping is to avoid monomer to gather in system too much, forms the product of particle diameter minimum.The more excellent consumption of initiator is the 0.1-0.3% of total amount.
5, monomer dropping complete after, under the said temperature condition, continue reaction 1-4h, make monomer reaction complete, then naturally cool to the room temperature discharging, namely obtain the microemulsion of high solids content.
Among the present invention, to the equal first underpressure distillation purifying and remove stopper under nitrogen atmosphere of monomer.Used monomer is methyl methacrylate (MMA), methacrylic acid (MAA), glycidyl methacrylate (GMA), methacrylic acid acetylacetic ester (AAEM), hydroxyethyl methylacrylate (HEMA), one or more of Rocryl 410 (HPMA) etc.General formula can be expressed as (chemical formula): H
2C=C (CH
3) COR.R is-O-CH
3Or-O-C-C (CH
3)-C-O or-O-C-C-OH or-O-C-C (O)-CH
3
The emulsifying agent that the present invention uses is: sodium lauryl sulphate (SDS), acrylamido sodium isopropyl xanthate (A-2405), contain allylic extraordinary ether alcohol sulfate (NRS-10), alkylphenol allyl polyether sulfate type anion surfactant (V-20S), one or more of OP series grade.
Emulsifying agent/assistant for emulsifying agent that the present invention uses is: the copolymerization product of silicon-containing monomer and vinyl monomer.Silicon-containing monomer is the one of the following kind: vinyltrimethoxy silane (A-171), and vinyltriethoxysilane (A-151), vinyl silane triisopropoxide (AC-76) etc., general formula can be expressed as (chemical formula): C=C-Si-R.R is-(OCH
3)
3Or-(OCH
2CH
3)
3Or-(OCH (CH
3)
2Vinyl monomer is the one of the following kind: vinylbenzene (St), and vinyl acetate between to for plastic (VAM), benzene divinyl (DVB) etc., general formula can be expressed as (chemical formula): C=C-R.R is-C
6H
6Or-C
6H
6-CH=CH
2
The initiator that the present invention uses is: Potassium Persulphate (KPS), ammonium persulphate (APS), azo two isonitrile (AIBN), benzoyl peroxide (BPO), one or more of dodecyl sodium sulfonate (ABS) etc.
The invention has the advantages that 1: with silicon-containing monomer and vinyl monomer multipolymer as Microemulsion Emulsifier/assistant for emulsifying agent, selection by polymerization technique and monomeric species, can effectively control the cross-linking density of emulsion particle, and can be so that the consumption of the emulsifying agent that uses in the whole reaction system or composite emulsifier significantly reduces, totally be lower than 2wt%, solved the too high problem of major defect-emulsifier in the micro-emulsion polymerization.2: total differential feeding mode has been adopted in present technique invention, efficiently solves traditional disposable feeding method and semicontinuous feeding method product viscosity is higher, the defective that particle diameter is larger.Whole monomers add fashionable in the differential mode, the particle diameter ratio monomer that obtains disposable (disposable feeding method) adds the particle diameter that obtains, and the particle diameter that (semicontinuous feeding method) adding obtains greater than in three batches reduces greatly, and product viscosity also has obvious decline.Total differential feeding method (slowly dripping) avoids monomer to gather in system too much, thereby makes the unstable or formation homopolymer of system, and makes monomer reaction complete, can obtain the more microemulsion of high solids content.Microemulsion by present method preparation has high solids content, low emulsifier, low viscous feature, and its polymer content can reach 50wt%, and emulsifier content is lower than 2wt%.Particle diameter 10nm-50nm.Polymer nano-particle can contain the multiple functional groups such as amido, hydroxyl, carboxyl, may crosslinked film forming under suitable condition.Can be widely used in encapsulated, new and high technology coating, support of the catalyst, waveguide material etc.
Performance to the microemulsion of the present invention preparation can characterize with the following method: the size of emulsion and distribute and adopt nanometer laser granularity and zeta potentiometric analyzer to measure; Being coated with film dynamic performance tests with the Instron electronic tension tester; The emulsion polymer structure is measured with Fourier infrared spectrograph (FTIR); Glass Transition Temperature of Latex is measured with differential scanning calorimeter (DSC); Minimum film-forming temperature uses minimum film-forming temperature to measure; The latex particle form of emulsion is measured with scanning electron microscope (TEM); The crosslinked MEK(methyl ethyl ketone that passes through of emulsion latex film) method of reflux extraction is measured; The pencil hardness of filming is measured by ASTM-3364; Sticking power is pressed GB/T9286-88 cross cross-hatching and is measured; The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
Embodiment
Below in conjunction with example, the present invention is described in further detail.
Embodiment 1: with the high solids content micro-emulsion polymerization of the synthetic P (St-AC76) of ATRP method as emulsifying agent/assistant for emulsifying agent.
Polymerization procedure:
(1) preparation of P (St-AC76)
In the four-hole boiling flask that thermometer, magnetic stir bar are housed, add styrene monomer 20g, the alpha-brominated isopropylformic acid hydroxyl of initiator ethyl ester, solvent pimelinketone, 0.335g Catalysts Cu Br, 0.80g part HMTETA mixes, and system is vacuumized logical nitrogen, at 90-95 ℃ of lower reaction 15h.After reaction finished, polymerisate dissolved with tetrahydrofuran (THF), removes copper salt catalyst, and the vacuum drying oven of putting into 60 ℃ is drying to obtain P (St-Br) macromole evocating agent.Take the preparation P (St-Br) as initiator, take CuBr and HMTETA as catalyst system, pimelinketone is solvent, reaction system is filled with nitrogen after repeatedly vacuumizing, in 105-110 ℃ of lower initiation silicon-containing monomer AC76 polymerization, after reaction finishes, polymerisate dissolves with tetrahydrofuran (THF), remove copper salt catalyst, be drying to obtain in the vacuum drying oven and prepare P (St-AC76) multipolymer, and with the assistant for emulsifying agent of this multipolymer as micro-emulsion polymerization.
(2) high solids content micro-emulsion polymerization
2.0gSDS is splashed in the initiation solution of P (St-AC76) for emulsifying agent/assistant for emulsifying agent, 70g deionized water composition of 0.3gAPS, the above-mentioned preparation of 1.0g, use ammoniacal liquor to regulate pH value to 7.To cause solution stirring and be warming up to 65 ℃, repeatedly logical nitrogen 5min deoxygenation in system, with whole monomer 25g hydroxyethyl methylacrylates (HEMA) slowly to be added dropwise to continuously in the system, 4h drips off, be warming up to simultaneously 72 ℃ of constant temperature, keep nitrogen atmosphere, stirring at low speed.Dropwise rear continuation at 72 ℃ of lower reaction 2h, make monomer reaction complete, finish reaction.Continue stirring and naturally cool to the room temperature discharging, product is the transparent liquid of blueing light, and particle diameter is 22.0nm.
Embodiment 2: with the high solids content micro-emulsion polymerization of the synthetic P (St-AC76) of RAFT method as emulsifying agent/assistant for emulsifying agent.
Polymerization procedure:
(1) preparation of P (St-AC76)
1. the preparation of macromolecular chain transfer agent
Get vinylbenzene, dithio naphthoic acid isopropyl cyanide ester, AIBN (mass ratio: 200:2:1), fully dissolving mixes and is placed in the ampere bottle, repeatedly vacuumize, sealing, heating in water bath is in 70 ℃ of reactions, reacting completely is placed in the refrigerator.Add an amount of tetrahydrofuran (THF) dissolve polymer after reaction finishes, dropwise be added drop-wise in the flask that methyl alcohol is housed, with precipitation method with purification of products after the suction filtration oven dry, further purify with soxhlet extraction again, vacuum-drying is to constant weight.
2. the preparation of silicon-containing monomer multipolymer
Take by weighing the macromolecular chain transfer agent after the 0.16g vacuum-drying, add the 3.2g vinyl silane triisopropoxide, and add 0.08gAIBN, sealing.Repeatedly vacuumize, under nitrogen protection, carry out.
(2) high solids content micro-emulsion polymerization
1.0gSDS is splashed in the initiation solution of P (St-AC76) for emulsifying agent/assistant for emulsifying agent, 70g deionized water composition of 0.1gAPS, the above-mentioned preparation of 1.0g, use ammoniacal liquor to regulate pH value to 7.To cause solution stirring and be warming up to 65 ℃, repeatedly logical nitrogen 5min deoxygenation in system, with whole monomer 25g hydroxyethyl methylacrylates (HEMA) slowly to be added dropwise to continuously in the system, 4h drips off, be warming up to simultaneously 72 ℃ of constant temperature, keep nitrogen atmosphere, stirring at low speed.Dropwise rear continuation at 72 ℃ of lower reaction 2h, make monomer reaction complete, finish reaction.Continue stirring and naturally cool to the room temperature discharging, product is the transparent liquid of blueing light, and particle diameter is 20.0nm.
Embodiment 3: with the high solids content micro-emulsion polymerization of the synthetic P (St-A151) of ATRP method as emulsifying agent/assistant for emulsifying agent.
Polymerization procedure:
(1) preparation of P (St-A151) is with embodiment 1.
(2) high solids content micro-emulsion polymerization
3.0gSDS is splashed in the initiation solution of P (St-A151) for emulsifying agent/assistant for emulsifying agent, 85g deionized water composition of 0.5gAPS, the above-mentioned preparation of 3.0g, use ammoniacal liquor to regulate pH value to 7.To cause solution stirring and be warming up to 65 ℃, repeatedly logical nitrogen 5min deoxygenation in system, with whole monomer 10g hydroxyethyl methylacrylates (HEMA) slowly to be added dropwise to continuously in the system, 4h drips off, be warming up to simultaneously 72 ℃ of constant temperature, keep nitrogen atmosphere, stirring at low speed.Dropwise rear continuation at 72 ℃ of lower reaction 2h, make monomer reaction complete, finish reaction.Continue stirring and naturally cool to the room temperature discharging, product is the transparent liquid of blueing light, and particle diameter is 25.0nm.
Embodiment 4: with the high solids content micro-emulsion polymerization of the synthetic P (VAc-AC76) of ATRP method as emulsifying agent/assistant for emulsifying agent.
Polymerization procedure:
(1) preparation of P (VAc-AC76)
In the four-hole boiling flask that thermometer, magnetic stir bar are housed, add Vinyl Acetate Monomer 20g, the alpha-brominated isopropylformic acid hydroxyl of initiator ethyl ester, solvent pimelinketone, 0.335g Catalysts Cu Br, 0.80g part HMTETA mixes, and system is vacuumized logical nitrogen, at 90-95 ℃ of lower reaction 15h.After reaction finished, polymerisate dissolved with THF, removes copper salt catalyst, and the vacuum drying oven of putting into 60 ℃ is drying to obtain P (VAc-Br) macromole evocating agent.Take the preparation P (VAc-Br) as initiator, take CuBr and HMTETA as catalyst system, pimelinketone is solvent, reaction system is filled with nitrogen after repeatedly vacuumizing, in 105-110 ℃ of lower initiation silicon-containing monomer AC76 polymerization, after reaction finishes, polymerisate dissolves with THF, remove copper salt catalyst, be drying to obtain in the vacuum drying oven and prepare P (VAc-AC76) multipolymer, and with the assistant for emulsifying agent of this multipolymer as micro-emulsion polymerization.
(2) high solids content micro-emulsion polymerization
2.0gSDS is splashed in the initiation solution of P (VAc-AC76) for emulsifying agent/assistant for emulsifying agent, 50g deionized water composition of 0.3gAPS, the above-mentioned preparation of 1.0g, use ammoniacal liquor to regulate pH value to 7.To cause solution stirring and be warming up to 65 ℃, repeatedly logical nitrogen 5min deoxygenation in system, with whole monomer 45g hydroxyethyl methylacrylates (HEMA) slowly to be added dropwise to continuously in the system, 4h drips off, be warming up to simultaneously 72 ℃ of constant temperature, keep nitrogen atmosphere, stirring at low speed.Dropwise rear continuation at 72 ℃ of lower reaction 2h, make monomer reaction complete, finish reaction.Continue stirring and naturally cool to the room temperature discharging, product is the transparent liquid of blueing light, and particle diameter is 55.0nm.
Embodiment 5: with the high solids content micro-emulsion polymerization of the synthetic P (VAc-A171) of RAFT method as emulsifying agent/assistant for emulsifying agent.
Polymerization procedure:
(1) preparation of P (VAc-A171)
1. the preparation of macromolecular chain transfer agent
Get vinyl acetate, dithio naphthoic acid isopropyl cyanide ester, AIBN (mass ratio: 200:2:1), fully dissolving mixes and is placed in the ampere bottle, repeatedly vacuumize, sealing, heating in water bath is in 70 ℃ of reactions, reacting completely is placed in the refrigerator.Add an amount of tetrahydrofuran (THF) dissolve polymer after reaction finishes, dropwise be added drop-wise in the flask that methyl alcohol is housed, with precipitation method with purification of products after the suction filtration oven dry, further purify with soxhlet extraction again, vacuum-drying is to constant weight.
2. the preparation of silicon-containing monomer multipolymer
Take by weighing the macromolecular chain transfer agent after the 0.16g vacuum-drying, add the 3.2g vinyltrimethoxy silane, and add 0.08gAIBN, sealing.Repeatedly vacuumize, under nitrogen protection, carry out.
(2) high solids content micro-emulsion polymerization
2.0gSDS is splashed in the initiation solution of P (VAc-A171) for emulsifying agent/assistant for emulsifying agent, 70g deionized water composition of 0.3gAPS, the above-mentioned preparation of 1.0g, use ammoniacal liquor to regulate pH value to 7.To cause solution stirring and be warming up to 65 ℃, repeatedly logical nitrogen 5min deoxygenation in system, with whole monomer 25g hydroxyethyl methylacrylates (HEMA) slowly to be added dropwise to continuously in the system, 4h drips off, be warming up to simultaneously 72 ℃ of constant temperature, keep nitrogen atmosphere, stirring at low speed.Dropwise rear continuation at 72 ℃ of lower reaction 2h, make monomer reaction complete, finish reaction.Continue stirring and naturally cool to the room temperature discharging, product is the transparent liquid of blueing light, and particle diameter is 30.0nm.
Embodiment 6: with the high solids content micro-emulsion polymerization of the synthetic P (VAc-A171) of ATRP method as emulsifying agent/assistant for emulsifying agent.
Polymerization procedure:
(1) preparation of P (VAc-A171) is with embodiment 4
(2) high solids content micro-emulsion polymerization
2.0gSDS is splashed in the initiation solution of P (VAc-A171) for emulsifying agent/assistant for emulsifying agent, 70g deionized water composition of 0.3gAPS, the above-mentioned preparation of 1.0g, use ammoniacal liquor to regulate pH value to 7.To cause solution stirring and be warming up to 65 ℃, repeatedly logical nitrogen 5min deoxygenation in system, with whole monomer 25g hydroxyethyl methylacrylates (HEMA) slowly to be added dropwise to continuously in the system, 4h drips off, be warming up to simultaneously 72 ℃ of constant temperature, keep nitrogen atmosphere, stirring at low speed.Dropwise rear continuation at 72 ℃ of lower reaction 2h, make monomer reaction complete, finish reaction.Continue stirring and naturally cool to the room temperature discharging, product is the transparent liquid of blueing light, and particle diameter is 38.0nm.
Embodiment 7: with the high solids content micro-emulsion polymerization of the synthetic P (DVB-AC76) of ATRP method as emulsifying agent/assistant for emulsifying agent.
Polymerization procedure:
(1) preparation of P (DVB-AC76)
In the four-hole boiling flask that thermometer, magnetic stir bar are housed, add DVB monomer 20g, the alpha-brominated isopropylformic acid hydroxyl of initiator ethyl ester, solvent pimelinketone, 0.335g Catalysts Cu Br, 0.80g part HMTETA mixes, and system is vacuumized logical nitrogen, at 90-95 ℃ of lower reaction 15h.After reaction finished, polymerisate dissolved with THF, removes copper salt catalyst, and the vacuum drying oven of putting into 60 ℃ is drying to obtain P (DVB-Br) macromole evocating agent.Take the preparation P (DVB-Br) as initiator, take CuBr and HMTETA as catalyst system, pimelinketone is solvent, reaction system is filled with nitrogen after repeatedly vacuumizing, in 105-110 ℃ of lower initiation silicon-containing monomer AC76 polymerization, after reaction finishes, polymerisate dissolves with THF, remove copper salt catalyst, be drying to obtain in the vacuum drying oven and prepare P (DVB-AC76) multipolymer, and with the assistant for emulsifying agent of this multipolymer as micro-emulsion polymerization.
(2) high solids content micro-emulsion polymerization
1.0gSDS is splashed in the initiation solution of P (DVB-AC76) for emulsifying agent/assistant for emulsifying agent, 70g deionized water composition of 0.3gAPS, the above-mentioned preparation of 1.0g, use ammoniacal liquor to regulate pH value to 7.To cause solution stirring and be warming up to 65 ℃, repeatedly logical nitrogen 5min deoxygenation in system, with whole monomer 25g hydroxyethyl methylacrylates (HEMA) slowly to be added dropwise to continuously in the system, 4h drips off, be warming up to simultaneously 72 ℃ of constant temperature, keep nitrogen atmosphere, stirring at low speed.Dropwise rear continuation at 72 ℃ of lower reaction 2h, make monomer reaction complete, finish reaction.Continue stirring and naturally cool to the room temperature discharging, product is the transparent liquid of blueing light, and particle diameter is 29.0nm.
Embodiment 8: with the high solids content micro-emulsion polymerization of the synthetic P (DVB-A171) of ATRP method as emulsifying agent/assistant for emulsifying agent.
Polymerization procedure:
(1) preparation of P (DVB-A171) is with embodiment 7
(2) high solids content micro-emulsion polymerization
2.0gSDS is splashed in the initiation solution of P (DVB-A171) for emulsifying agent/assistant for emulsifying agent, 70g deionized water composition of 0.3gAPS, the above-mentioned preparation of 1.0g, use ammoniacal liquor to regulate pH value to 7.To cause solution stirring and be warming up to 65 ℃, repeatedly logical nitrogen 5min deoxygenation in system, with whole monomer 25g methyl methacrylates (MMA) slowly to be added dropwise to continuously in the system, 4h drips off, be warming up to simultaneously 72 ℃ of constant temperature, keep nitrogen atmosphere, stirring at low speed.Dropwise rear continuation at 72 ℃ of lower reaction 2h, make monomer reaction complete, finish reaction.Continue stirring and naturally cool to the room temperature discharging, product is the transparent liquid of blueing light, and particle diameter is 26.0nm.
Embodiment 9: with the high solids content micro-emulsion polymerization of the synthetic P (DVB-A151) of ATRP method as emulsifying agent/assistant for emulsifying agent.
Polymerization procedure:
(1) preparation of P (DVB-A151) is with embodiment 7
(2) high solids content micro-emulsion polymerization
1.0gSDS is splashed in the initiation solution of P (DVB-A151) for emulsifying agent/assistant for emulsifying agent, 70g deionized water composition of 0.3gAPS, the above-mentioned preparation of 2.0g, use ammoniacal liquor to regulate pH value to 7.To cause solution stirring and be warming up to 65 ℃, repeatedly logical nitrogen 5min deoxygenation in system, whole monomer 25g hydroxyethyl methylacrylates (HEMA) and glycidyl methacrylate (GMA) is composite, compound proportion (1:1) is slowly to be added dropwise to continuously in the system, 4h drips off, be warming up to simultaneously 72 ℃ of constant temperature, keep nitrogen atmosphere, stirring at low speed.Dropwise rear continuation at 72 ℃ of lower reaction 2h, make monomer reaction complete, finish reaction.Continue stirring and naturally cool to the room temperature discharging, product is the transparent liquid of blueing light, and particle diameter is 32.0nm.
Claims (10)
1. high-solid content polymer method for synthesizing microemulsion: it is characterized in that step is as follows:
(1) with silicon-containing monomer and vinyl monomer copolymerization multipolymer as emulsifying agent/assistant for emulsifying agent;
(2) with the water-soluble water that becomes of emulsifying agent;
(3) emulsifying agent/assistant for emulsifying agent synthetic in (1) is dissolved in monomer and is mixed into oil phase;
(4) in aqueous phase solution, add initiator, slowly drip continuously the oil-phase solution polymerization and get the microemulsion product.
2. described high-solid content polymer method for synthesizing microemulsion according to claim 1 is characterized in that step is as follows:
(1) silicon-containing monomer and vinyl monomer are used the active free radical polymerization method synthetic copolymer;
The emulsifiers dissolve that (2) will account for total amount 1-3% becomes water in the deionized water that accounts for total amount 50-90%;
(3) will account for total amount 1-3% multipolymer emulsifying agent/assistant for emulsifying agent is dissolved in and accounts for one kind of total amount 10-50% or more than one monomers are mixed into oil phase;
(4) water is added be connected in the four-hole boiling flask of prolong and agitator, add and account for total amount 0.1-0.5% initiator, logical nitrogen is also kept 72 ℃, and oil phase is added polymerization 5-6h in the reaction system in the differential mode, naturally cools to discharging after the room temperature.
3. described high-solid content polymer method for synthesizing microemulsion according to claim 2, it is characterized in that silicon-containing monomer and vinyl monomer use free radical polymerisation process synthetic copolymer in the step (1), free radical polymerisation process can be selected from the one of the following kind: atom transfer radical polymerization, reversible addition-fracture chain transfer polymerization causes-shift-stops active free radical polymerization or common radical polymerization.
4. described high-solid content polymer method for synthesizing microemulsion according to claim 2, it is characterized in that silicon-containing monomer and vinyl monomer use free radical polymerisation process synthetic copolymer in the step (2), silicon-containing monomer can be selected from the one of the following kind: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide; Vinyl monomer can be selected from the one of the following kind: vinylbenzene, vinyl acetate, benzene divinyl.
5. described high-solid content polymer method for synthesizing microemulsion according to claim 2 is characterized in that the described emulsifying agent of step (2) can be selected from anionic emulsifier, nonionic emulsifier or negatively charged ion and nonionic compound emulsifying agent; Anionic emulsifier is: one or more mixtures of sodium lauryl sulphate, Sodium palmityl sulfate, Sodium dodecylbenzene sulfonate, oxyethyl group phenolic ether sodium sulfate; Nonionic emulsifier is: one or more mixtures of OP series; Negatively charged ion and nonionic compound emulsifying agent are above-mentioned two or more mixture.
6. described high-solid content polymer method for synthesizing microemulsion according to claim 2 is characterized in that the described emulsifying agent/assistant for emulsifying agent of step (3) can be selected from the synthetic relevant copolymerized polymer of step (1).
7. described high-solid content polymer method for synthesizing microemulsion according to claim 2, it is characterized in that the described initiator of step (5) is water soluble starter or oil-soluble initiator, water soluble starter is: Potassium Persulphate, ammonium persulphate, water soluble oxidized-reduction initiating system; Oil-soluble initiator is: Diisopropyl azodicarboxylate, dibenzoyl peroxide etc.
8. described high-solid content polymer method for synthesizing microemulsion according to claim 1, it is characterized in that the emulsifying agent/assistant for emulsifying agent that uses is vinyltrimethoxy silane, vinyltriethoxysilane, the multipolymer of a kind of and vinyl monomer of vinyl silane triisopropoxide etc.; Vinyl monomer is: vinylbenzene, vinyl acetate, benzene divinyl etc. a kind of.
9. described high-solid content polymer method for synthesizing microemulsion according to claim 1, the consumption that it is characterized in that monomer is the 30-50% of total amount.
10. described high-solid content polymer method for synthesizing microemulsion according to claim 1, the consumption that it is characterized in that initiator is the 0.1-0.3% of total amount.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108997519A (en) * | 2018-08-03 | 2018-12-14 | 上海保立佳新材料有限公司 | A kind of water resistance ultra-fine grain diameter acrylic acid ester emulsion and preparation method thereof |
| CN109251281A (en) * | 2018-09-17 | 2019-01-22 | 西安天亿胶粘材料有限公司 | A kind of preparation method of the easily peelable printing emulsion type resin of high temperature resistant |
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| CN1272502A (en) * | 2000-05-30 | 2000-11-08 | 复旦大学 | High solid content nanometer polymer micro emulsion synthesizing method |
| CN102108106A (en) * | 2011-01-05 | 2011-06-29 | 常州大学 | Method for preparing microcapsule through miniemulsion polymerization by utilizing siloxane copolymer as auxiliary stabilizing agent |
| CN102585042A (en) * | 2012-01-12 | 2012-07-18 | 常州大学 | Application of the silicon-containing block polymer |
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| CN102108106A (en) * | 2011-01-05 | 2011-06-29 | 常州大学 | Method for preparing microcapsule through miniemulsion polymerization by utilizing siloxane copolymer as auxiliary stabilizing agent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997519A (en) * | 2018-08-03 | 2018-12-14 | 上海保立佳新材料有限公司 | A kind of water resistance ultra-fine grain diameter acrylic acid ester emulsion and preparation method thereof |
| CN109251281A (en) * | 2018-09-17 | 2019-01-22 | 西安天亿胶粘材料有限公司 | A kind of preparation method of the easily peelable printing emulsion type resin of high temperature resistant |
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