CN102653583B - Preparation method of amphiphilic segmented copolymer - Google Patents
Preparation method of amphiphilic segmented copolymer Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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Abstract
The invention discloses a preparation method of an amphiphilic segmented copolymer, and the method comprises the following steps of: preparing seed microemulsion and a pre-emulsified mixed monomer, triggering the seed microemulsion to have a microemulsion polymerization reaction, adding the pre-emulsified mixed monomer to obtain an acrylate polymer, and reacting the acrylate polymer with a hydrophilic monomer, to obtain the amphiphilic segmented copolymer. In the preparation method, the microemulsion polymerization is stable in reaction thermodynamics system, and the dispersed phase is smaller in size, according to the preparation method, the granularity of the polymer emulsion can be evenly distributed, and the emulsion is stable in performance. The segmented copolymer synthesized by the method has better appetency to the hydrophilic fiber and the hydrophobic dye, so that the surface of the natural fiber can be improved, and simultaneously the organic dye dispersing system is good in stability.
Description
Technical field
The present invention relates to the prize pigment dispersing agent of film of liquid-crystal display, be specifically related to a kind of method of preparing amphiphilic block copolymer.
Background technology
Amphiphilic block copolymer refers to and in same polymer, had both contained hydrophilic segment, contains again the multipolymer of hydrophobic segment.With common polymer phase ratio, amphiphilic block copolymer has many special propertys, as surfactivity, lyotropy and thickening property.
Letex polymerization (emulsion polymerization) is a kind of synthetic method conventional in Polymer Synthesizing process, because it is with water as solvent, very favourable to environment.Emulsion polymerization is under the effect of emulsifying agent and by mechanical stirring, makes monomer in water, be dispersed into milk sap, by initiator, is caused and the polyreaction of carrying out.
Chinese patent application CN 101870759A discloses a kind of method of synthesis of amphoteric segmented copolymer, and what this method adopted is common emulsion polymerization synthesis of amphoteric block polymer.Yet this emulsion is muddy Unstable Systems, and its thermodynamic system is unstable, and dispersed phase size is larger, makes chemical reaction system unstable, and the distribution of pigment particle size and stability are had a certain impact.
Summary of the invention
The technical problem to be solved in the present invention is the thermodynamic stability that how to strengthen amphiphilic block copolymer system.
In order to solve the problems of the technologies described above, the invention provides a kind of method of preparing amphiphilic block copolymer.
The method that the present invention prepares amphiphilic block copolymer comprises the steps: to prepare seed microemulsion and pre-emulsification mix monomer, Priming Seeds microemulsion carries out microemulsion reaction, add pre-emulsification mix monomer to obtain acrylic ester polymer, it is reacted with hydrophilic monomer, obtain amphiphilic block copolymer.
Described seed microemulsion is prepared as follows: 60～75% emulsifying agent is mixed with water, by magnetic agitation, obtain emulsion, add 25～40% acrylic acid or the like hydrophobic monomer under ultrasonic agitation, obtain seed microemulsion.
Wherein, the volume ratio of emulsifying agent, water, acrylic acid or the like hydrophobic monomer is preferably (1～2): (25～50): (10～20); The rotating speed of magnetic agitation is 300～330rad/min; The time of magnetic agitation is 25～35min.
Described pre-emulsification mix monomer is prepared as follows: 25～40% emulsifying agent is mixed with water, add 60～75% acrylic acid or the like hydrophobic monomer under magnetic agitation, obtain pre-emulsification mix monomer.
Wherein the volume ratio of emulsifying agent, water, acrylic acid or the like hydrophobic monomer is preferably (1～2): (50～100): (50～80); The rotating speed of magnetic agitation is 400～430rad/min; The time of magnetic agitation is 25～35min.
Described acrylic ester polymer is prepared as follows: in seed microemulsion, add alkali, catalyzer, part and initiator, cause microemulsion; After presenting blue light, seed microemulsion is warming up to 80～85 ℃; Slowly drip pre-emulsification mix monomer; In 2～3h, drip off, after insulation slaking 0.5～1h, lower the temperature, regulating pH is 9～11, and reaction product is vacuumized, cooling under shielding gas, suction filtration, and washing, dry, obtain acrylic ester polymer.
Wherein, the volume ratio of seed microemulsion used, pre-emulsification mix monomer, alkali, catalyzer, part, initiator is preferably (72～144): (101～182): (0.05～0.15): (1～2): (2～3): (1～2).
By acrylic ester polymer is mixed with hydrophilic monomer, under shielding gas, in water-bath, react 50～80min, cooling, suction filtration, washing, dry, obtain amphiphilic block copolymer.
Wherein, the temperature of water-bath is 25～35 ℃; The volume ratio of acrylic ester polymer and hydrophilic monomer is 1: (2～4).
Described acrylic acid or the like hydrophobic monomer is selected from one or more in methyl acrylate, ethyl propenoate, isobutyl acrylate, methyl methacrylate and β-dimethyl-aminoethylmethacrylate.
Described hydrophilic monomer is selected from one or more in acrylamide, Methacrylamide, propylene glycol and glycerol.
Described initiator is selected from persulphate or hydrogen peroxide or derivatives thereof.Preferably, described initiator is Sodium Persulfate or Potassium Persulphate.
Described emulsifying agent is selected from one or more in Teepol, Sodium dodecylbenzene sulfonate and triton x-100.
Described catalyzer is selected from one or more in cupric bromide, iron bromide, cupric chloride and iron(ic) chloride.
Described part is selected from 2-methyl-5-vinylpyrine, 3-vinyl pyridine, 4, a kind of in 4-dipyridyl and pentamethyl-diethylenetriamine.
Described alkali is selected from one or more in sodium bicarbonate, sodium carbonate and sodium hydroxide.
Described shielding gas is nitrogen or rare gas element.
The present invention is by adopting microemulsion polymerization method synthesis of amphoteric segmented copolymer.Micro-emulsion polymerization is less by the droplet size dispersion of disperse phase, can make the droplet diameter of disperse phase within the scope of 10～100nm.In microemulsion system, it is that one deck laminated film of forming by emulsifying agent and assistant for emulsifying agent and interfacial layer maintain that it is stable that microballon drips.
Because micro-emulsion polymerization has thermodynamically stable characteristic, and the less feature of dispersed phase size in microemulsion, the Amphiphilic Block Polymers system Thermodynamically stable that the present invention utilizes the polymerization of microemulsion method to obtain, dispersed phase size is less, between 21.5～33nm, even size distribution and stable.The amphiphilic block copolymer synthetic by this method has good avidity to hydrophilic fiber and hydrophobic pigment, can carry out modification to surface of natural fibers, there is to excellent stabilization in organic pigment dispersions system simultaneously.Therefore, can be used as the prize pigment dispersing agent of film of liquid-crystal display.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
The properties of the amphiphilic block copolymer that synthetic method of the present invention obtains can adopt following index to detect:
1. multipolymer viscosity: the viscosity that adopts BROOKFIELD DV-C digital display viscometer determining adhesive agent emulsion.
2. copolymer particle particle diameter and size distribution: the particle diameter and the size distribution that adopt Nano ZS particle size analyzer determination segmented copolymer emulsion.
3. molecular weight of copolymer and dispersion index: adopt Waters515 gel permeation chromatography test polymer molecular weight and molecular weight distribution, probe temperature is 25 ℃, and moving phase is tetrahydrofuran (THF), and flow velocity is 1.0ml/min, and standard is polystyrene.
For exemplary but the present invention is described without limitation, in following examples, acrylic acid or the like hydrophobic monomer is selected from methyl acrylate, isobutyl acrylate and methyl methacrylate; Hydrophilic monomer is selected from acrylamide, Methacrylamide and propylene glycol; Initiator is selected from Sodium Persulfate and Potassium Persulphate; Emulsifying agent is selected from Teepol and Sodium dodecylbenzene sulfonate; Catalyzer is selected from cupric bromide and iron bromide; Part is selected from 2-methyl-5-vinylpyrine, 3-vinyl pyridine and 4,4-dipyridyl; Alkali used is selected from sodium bicarbonate and sodium carbonate.
For exemplary but the present invention is described without limitation, in following examples, when preparing seed microemulsion, the volume ratio of emulsifying agent, water, acrylic acid or the like hydrophobic monomer is (1～2): (25～50): (10～20); When preparation pre-emulsification mix monomer, the volume ratio of emulsifying agent, water, acrylic acid or the like hydrophobic monomer is (1～2): (50～100): (50～80); When preparing acrylic ester polymer, the volume ratio of seed microemulsion used, pre-emulsification mix monomer, alkali, catalyzer, part, initiator is (72～144): (101～182): (0.05～0.15): (1～2): (2～3): (1～2); The volume ratio of acrylic ester polymer and hydrophilic monomer is 1: (2～4).
Embodiment 1
(1) 4ml Teepol, 100ml deionized water are joined in band side-tube flask, under the magnetic agitation that is 300rad/min at rotating speed, stir 30min and obtain emulsion, under ultrasonic stirring, add 30ml methyl acrylate to obtain translucent seed microemulsion;
(2) 2ml Teepol, 100ml deionized water are joined in band side-tube flask, add 60ml methyl acrylate at rotating speed under the magnetic agitation that is 400rad/min, magnetic agitation 30min obtains pre-emulsification mix monomer;
(3) in the seed microemulsion obtaining to step (1), add 0.1ml sodium carbonate, 2ml cupric bromide, 2ml 2-methyl-5-vinylpyrine, 2ml Sodium Persulfate, cause microemulsion; After seed microemulsion presents blue light, be warming up to 85 ℃, slowly drip the pre-emulsification mix monomer that step (2) obtains, in 2h, drip off, after insulation slaking 0.5h, lower the temperature, regulate pH to 10, reaction product sealing is vacuumized, make vacuum tightness reach after 40kPa again applying argon gas to normal pressure, three times repeatedly; Under argon gas existence condition, by reaction product cooling 20min in frozen water, to greenhouse cooling to 20 ℃, reaction product is carried out to suction filtration; The solid that suction filtration obtains deionized water rinsing 3 times, under 50 ℃ of conditions, vacuum drying 4h obtains acrylic ester polymer;
(4) 1 part of (250ml) acrylic ester polymer and 2 parts of (500ml) Methacrylamides are mixed in band side-tube flask, sealing vacuumizes, and makes vacuum tightness reach after 20kPa applying argon gas to normal pressure, three times repeatedly again; Under condition under argon gas exists, flask is put into 30 ℃ of water-baths and react 50min, take out flask and put into the cooling 30min of ice-water bath, be down to 20 ℃ to temperature, migrate out the reaction product the suction filtration that obtain, by the solid obtaining, with after deionized water rinsing 4 times, under 50 ℃ of conditions, vacuum drying 4h obtains amphiphilic block copolymer.
Embodiment 2
(1) 2ml Sodium dodecylbenzene sulfonate, 50ml deionized water are joined in band side-tube flask, under the magnetic agitation that is 330rad/min at rotating speed, stir 30min and obtain emulsion, under ultrasonic stirring, add 20ml methyl acrylate to obtain translucent seed microemulsion;
(2) 1ml Sodium dodecylbenzene sulfonate, 50ml deionized water are joined in band side-tube flask, add 50ml methyl acrylate at rotating speed under the magnetic agitation that is 430rad/min, magnetic agitation 30min obtains pre-emulsification mix monomer;
(3) in the seed microemulsion obtaining to step (1), add 0.05ml sodium carbonate, 1ml cupric bromide, 2ml 3-vinyl pyridine, 1ml Potassium Persulphate, cause microemulsion; After seed microemulsion presents blue light, be warming up to 85 ℃, slowly drip the pre-emulsification mix monomer that step (2) obtains, in 2h, drip off, after insulation slaking 0.5h, lower the temperature, regulate pH to 10, reaction product sealing is vacuumized, make vacuum tightness reach after 40kPa again applying argon gas to normal pressure, three times repeatedly; Under argon gas existence condition, by reaction product cooling 20min in frozen water, to greenhouse cooling to 20 ℃, reaction product is carried out to suction filtration; The solid that suction filtration obtains deionized water rinsing 3 times, under 50 ℃ of conditions, vacuum drying 4h obtains acrylic ester polymer;
(4) 1 part of (100ml) acrylic ester polymer and 2 parts of (200ml) propylene glycol are mixed in band side-tube flask, sealing vacuumizes, and makes vacuum tightness reach after 20kPa applying argon gas to normal pressure, three times repeatedly again; Under condition under argon gas exists, flask is put into 30 ℃ of water-baths and react 50min, take out flask and put into the cooling 30min of ice-water bath, be down to 20 ℃ to temperature, migrate out the reaction product the suction filtration that obtain, by the solid obtaining, with after deionized water rinsing 4 times, under 50 ℃ of conditions, vacuum drying 4h obtains amphiphilic block copolymer.
Embodiment 3
(1) 6ml Teepol, 150ml deionized water are joined in band side-tube flask, under the magnetic agitation that is 300rad/min at rotating speed, stir 35min and obtain emulsion, under ultrasonic stirring, add 45ml methyl methacrylate to obtain translucent seed microemulsion;
(2) 3ml Teepol, 150ml deionized water are joined in band side-tube flask, add 90ml methyl methacrylate at rotating speed under the magnetic agitation that is 400rad/min, magnetic agitation 30min obtains pre-emulsification mix monomer;
(3) in the seed microemulsion obtaining to step (1), add 0.15ml sodium bicarbonate, 2ml iron bromide, 3ml 4,4-dipyridyl, 2ml Sodium Persulfate, cause microemulsion; After seed microemulsion presents blue light, be warming up to 80 ℃, slowly drip the pre-emulsification mix monomer that step (2) obtains, in 3h, drip off, after insulation slaking 1h, lower the temperature, regulate pH to 9, reaction product sealing is vacuumized, make vacuum tightness reach after 40kPa again applying argon gas to normal pressure, three times repeatedly; Under argon gas existence condition, by reaction product cooling 15min in frozen water, to greenhouse cooling to 20 ℃, reaction product is carried out to suction filtration; The solid that suction filtration obtains deionized water rinsing 3 times, under 50 ℃ of conditions, vacuum drying 4h obtains acrylic ester polymer;
(4) 1 part of (400ml) acrylic ester polymer and 2 parts of (800ml) acrylamides are mixed in band side-tube flask, sealing vacuumizes, and makes vacuum tightness reach after 20kPa applying argon gas to normal pressure, three times repeatedly again; Under condition under argon gas exists, flask is put into 25 ℃ of water-baths and react 60min, take out flask and put into the cooling 30min of ice-water bath, be down to 20 ℃ to temperature, migrate out the reaction product the suction filtration that obtain, by the solid obtaining, with after deionized water rinsing 4 times, under 50 ℃ of conditions, vacuum drying 4h obtains amphiphilic block copolymer.
Embodiment 4
(1) 40ml Sodium dodecylbenzene sulfonate, 1000ml deionized water are joined in band side-tube flask, under the magnetic agitation that is 320rad/min at rotating speed, stir 25min and obtain emulsion, under ultrasonic stirring, add 300ml isobutyl acrylate to obtain translucent seed microemulsion;
(2) 20ml Sodium dodecylbenzene sulfonate, 1000ml deionized water are joined in band side-tube flask, add 600ml isobutyl acrylate at rotating speed under the magnetic agitation that is 420rad/min, magnetic agitation 30min obtains pre-emulsification mix monomer;
(3) in the seed microemulsion obtaining to step (1), add 1ml sodium carbonate, 20ml cupric bromide, 20ml 3-vinyl pyridine, 20ml Potassium Persulphate, cause microemulsion; After seed microemulsion presents blue light, be warming up to 85 ℃, slowly drip the pre-emulsification mix monomer that step (2) obtains, in 2h, drip off, after insulation slaking 0.5h, lower the temperature, regulate pH to 11, reaction product sealing is vacuumized, make vacuum tightness reach after 40kPa again inflated with nitrogen to normal pressure, three times repeatedly; Under nitrogen existence condition, by reaction product cooling 20min in frozen water, to greenhouse cooling to 20 ℃, reaction product is carried out to suction filtration; The solid that suction filtration obtains deionized water rinsing 3 times, under 50 ℃ of conditions, vacuum drying 4h obtains acrylic ester polymer;
(4) 1 part of (1200ml) acrylic ester polymer and 2 parts of (2400ml) propylene glycol are mixed in band side-tube flask, sealing vacuumizes, and makes vacuum tightness reach after 20kPa inflated with nitrogen to normal pressure, three times repeatedly again; Under condition under nitrogen exists, flask is put into 25 ℃ of water-baths and react 80min, take out flask and put into the cooling 30min of ice-water bath, be down to 20 ℃ to temperature, migrate out the reaction product the suction filtration that obtain, by the solid obtaining, with after deionized water rinsing 4 times, under 50 ℃ of conditions, vacuum drying 4h obtains amphiphilic block copolymer.
The amphiphilic block copolymer that embodiment 1～4 is obtained carries out performance test, the results are shown in Table 1:
Table 1
As shown in Table 1, amphiphilic block copolymer prepared by the present invention, its particle diameter distribution width is between 21.5～33nm, and dispersed phase size scope is less; Gained amphiphilic block copolymer has good avidity to hydrophilic fiber and hydrophobic pigment, and its dispersion stabilization can characterize by the long-term follow test to the viscosity of pigment and granularity.In half a year, to year, when the prepared amphiphilic block copolymer of the inventive method is used as pigment dispersing agent, there is obvious growth in the viscosity of pigment and granularity, illustrates that it has good stability hardly.
As known by the technical knowledge, the present invention can realize by other the embodiment that does not depart from its spirit or essential feature.Therefore, above-mentioned disclosed embodiment, with regard to each side, just illustrates, and is not only.Change within the scope of the present invention all or within being equal to scope of the present invention is all contained in protection scope of the present invention.
Claims (7)
1. a method of preparing amphiphilic block copolymer, it is characterized in that, comprise the steps: to prepare seed microemulsion and pre-emulsification mix monomer, Priming Seeds microemulsion carries out microemulsion reaction, add pre-emulsification mix monomer to obtain acrylic ester polymer, it is reacted with hydrophilic monomer, obtain amphiphilic block copolymer;
Described seed microemulsion is prepared as follows: 60～75% emulsifying agent is mixed with water, by magnetic agitation, obtain emulsion, add 25～40% acrylic acid or the like hydrophobic monomer under ultrasonic agitation, obtain seed microemulsion; The volume ratio of emulsifying agent, water, acrylic acid or the like hydrophobic monomer is (1～2): (25～50): (10～20);
Described pre-emulsification mix monomer is prepared as follows: 25～40% emulsifying agent is mixed with water, add 60～75% acrylic acid or the like hydrophobic monomer under magnetic agitation, obtain pre-emulsification mix monomer; The volume ratio of emulsifying agent, water, acrylic acid or the like hydrophobic monomer is (1～2): (50～100): (50～80);
Described acrylic ester polymer is prepared as follows: in described seed microemulsion, add alkali, catalyzer, part and initiator, cause microemulsion; After presenting blue light, seed microemulsion is warming up to 80～85 ℃; Slowly drip described pre-emulsification mix monomer; In 2～3h, drip off, after insulation slaking 0.5～1h, lower the temperature, regulating pH is 9～11, and reaction product is vacuumized, cooling under shielding gas, suction filtration, and washing, dry, obtain acrylic ester polymer; The volume ratio of seed microemulsion used, pre-emulsification mix monomer, alkali, catalyzer, part, initiator is (72～144): (101～182): (0.05～0.15): (1～2): (2～3): (1～2).
2. method according to claim 1, is characterized in that, while preparing seed microemulsion, the rotating speed of magnetic agitation is 300～330rad/min, and the time of magnetic agitation is 25～35min.
3. method according to claim 1, is characterized in that, during preparation pre-emulsification mix monomer, the rotating speed of magnetic agitation is 400～430rad/min, and the time of magnetic agitation is 25～35min.
4. method according to claim 1, is characterized in that, by acrylic ester polymer is mixed with hydrophilic monomer, under shielding gas, reacts 50～80min in water-bath, cooling, suction filtration, and washing, dry, obtain amphiphilic block copolymer.
5. method according to claim 4, is characterized in that, the temperature of water-bath is 25～35 ℃.
6. method according to claim 4, is characterized in that, the volume ratio of acrylic ester polymer and hydrophilic monomer is 1:(2～4).
7. the amphiphilic block copolymer that the preparation method described in claim 1～6 any one obtains is as the application of pigment dispersing agent.
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| CN101870759A (en) * | 2010-06-24 | 2010-10-27 | 江南大学 | Synthesis method of amphiphilic block copolymer |
| CN102040711A (en) * | 2010-11-09 | 2011-05-04 | 华南理工大学 | Amphiphilic polymer pigment wetting dispersant for water-based coating and preparation method thereof |
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| CN101870759A (en) * | 2010-06-24 | 2010-10-27 | 江南大学 | Synthesis method of amphiphilic block copolymer |
| CN102040711A (en) * | 2010-11-09 | 2011-05-04 | 华南理工大学 | Amphiphilic polymer pigment wetting dispersant for water-based coating and preparation method thereof |
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| Title |
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| 郑根稳等.预乳化法制备纯丙微乳液.《孝感学院学报》.2006,第26卷(第6期),第12-14页. * |
| 预乳化法制备纯丙微乳液;郑根稳等;《孝感学院学报》;20061130;第26卷(第6期);第12-14页 * |
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