CN102936305A - Method for preparing branched polymer through suspension polymerization - Google Patents
Method for preparing branched polymer through suspension polymerization Download PDFInfo
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- CN102936305A CN102936305A CN2012104244928A CN201210424492A CN102936305A CN 102936305 A CN102936305 A CN 102936305A CN 2012104244928 A CN2012104244928 A CN 2012104244928A CN 201210424492 A CN201210424492 A CN 201210424492A CN 102936305 A CN102936305 A CN 102936305A
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Abstract
The invention discloses a method for preparing a branched polymer through suspension polymerization and belongs to the field of functional polymer preparation. A functional monomer containing polymerizable double bonds and chain transferring sulfydryl serves as a branching monomer, polyving akohol aqueous solution serves as the dispersing agent, azodiisobutyronitrile (AIBN) serves as the initiator, and styrene, (methyl) acrylate or vinyl acetate and the like serve as the monomers. The stirring speed is 300-500r/min, and branched polymer microspheres can be obtained successfully by performing polymerization for 3-12 hours under the temperature of 65-90 DEG C. The functional monomer containing polymerizable double bonds and chain transferring sulfydryl serves as the branching monomer, transparent branched polymeric microspheres even in grain size can be synthetized through suspension polymerization, and a polymerizing system is stable, easy to operate and capable of performing aftertreatment conveniently. The molecular weight of the branched polymer is high compared with solution polymerization, the molecular weight distribution is narrow, and the branching degree, the molecular weight and the molecular weight distribution are controllable.
Description
Technical field
The present invention relates to a kind of implementation method for preparing branched polymer: suspension polymerization is characterized in that the gained branched polymer is microballoon.Belong to Polymer Synthesizing, the functional polymer preparation field.
Background technology
Branched polymer is due to the three-dimensional ball-like structure of its uniqueness, therefore than simple linear polymer, there is lower melting viscosity and solution viscosity, can and improve polymer material molding processing characteristics etc. for the preparation of solventless coatings and polymers with high solids content solution.
The synthetic technology of branched polymer is mainly activity/controllable free-radical solution polymerization and the conventional free radical solution polymerization under chain forwarding function monomer exists at present.The molecular weight of these polyreaction gained branched polymers is relatively low, and molecular weight distribution is wider.The postprocessing working procedures of solution polymerization is comparatively loaded down with trivial details, consume a large amount of solvents and precipitation agent, and the polymkeric substance obtained is generally powder.Branched polymer when improving the polymer material molding processing characteristics, if add with the powder form, mixes inhomogeneously with body material (being generally pellet), and be difficult for plasticizing in molding process.These problems have limited the development of branched polymer mass-producing application to a certain extent.
Pursue the easy of synthetic method, cheap is an important directions of branched polymer research.It is low that suspension polymerization has reaction system viscosity, conducts heat and easy control of temperature; Molecular weight product and molecular weight distribution are more stable; The advantages such as postprocessing working procedures is simpler than letex polymerization and solution polymerization, and production cost is low.The suspension polymerization resulting polymers is microballoon, during with the body material forming process, easily mixes, easily plasticizing.
The present invention adopts that implementation condition is simple, the synthesizing branched polymkeric substance of suspension polymerization of convenient post-treatment, and expectation obtains that molecular weight is relatively high, molecular weight distribution is narrower, and has the branched polymer microballoon of the high degree of branching.This invention has great importance to branched polymer mass-producing application.
Summary of the invention
The invention discloses the method for the synthesizing branched polymkeric substance of a kind of suspension polymerization, the function monomer that it is characterized in that containing polymerizable double bond and chain transfer sulfydryl is branched monomer, the polyreaction implementation condition is simple, convenient post-treatment, the gained branched polymer is microballoon, and polymericular weight, molecular weight distribution and degree of branching can be controlled.
Suspension polymerization prepares the method for branched polymer, it is characterized in that carrying out according to following step: adopting the function monomer that contains polymerizable double bond and chain transfer sulfydryl is branched monomer, take polyvinyl alcohol water solution as dispersion agent, Diisopropyl azodicarboxylate (AIBN) is initiator, carry out suspension polymerization and obtain the uniform branched polymer microballoon of particle diameter under the stirring velocity of setting and polymerization temperature, stirring velocity is 300 ~ 500r/min, polymeric reaction temperature is controlled at 65 ~ 90 ℃, and polymerization reaction time is controlled as 3-12 hour.
Wherein said branched monomer: initiator: the molar feed ratio of polymerization single polymerization monomer is 0.25 ~ 2:0.5 ~ 3:100, the water of wherein said polyvinyl alcohol water solution: the mass ratio of polymerization single polymerization monomer (water-oil ratio) is 5 ~ 10:1.
The weight percent of the polyvinyl alcohol in wherein said polyethylene of dispersing agent alcohol solution is 0.24% ~ 0.35%.
Wherein said polymerization process is suspension polymerization, and polymerization mechanism is radical polymerization.
Wherein said branched monomer is the function monomer that has polymerizable double bond and chain transfer sulfydryl concurrently, is specially methacrylic acid-own ester of 3-sulfydryl or methacrylic acid sulfydryl propionyloxy ethyl ester, and structural formula is as follows:
(methacrylic acid sulfydryl propionyloxy ethyl ester).
Wherein said polymerization single polymerization monomer vinylbenzene, (methyl) acrylate or vinyl acetate etc.
The copolymerization that wherein said polymerization system is the monomer homopolymerizations such as vinylbenzene, (methyl) acrylate or vinyl acetate or these monomers.
Advantage of the present invention: the function monomer that contains polymerizable double bond and chain transfer sulfydryl of take is branched monomer, with suspension polymerization, has synthesized the uniform transparent branched polymer microballoon of particle diameter, and polymerization system is stable, simple to operate, convenient post-treatment.The molecular weight of gained branched polymer is high with respect to solution polymerization, narrow molecular weight distribution, and its degree of branching, molecular weight and molecular weight distribution are controlled.
The accompanying drawing explanation
Fig. 1 is embodiment 1,2, and the limiting viscosity of 4 gained branched polystyrenes and linear polystyrene thing is with the change of molecular weight figure.
The limiting viscosity that Fig. 2 is embodiment 5 gained branching polymethylmethacrylates and Linear Polymethyl methacrylate is with the change of molecular weight figure.
The limiting viscosity that Fig. 3 is embodiment 7 gained branching polyvinyl acetate (PVA) and line style polyvinyl acetate (PVA) is with the change of molecular weight figure.
Fig. 4 is embodiment 1,5, the branching factor of 6,7,8 gained branched polymers
g' with the variation diagram of molecular weight.(
g' be limiting viscosity (Intrinsic Viscosity) ratio of branched polymer and simple linear polymer under the same molecular amount
g'=IV
Branching / IV
Line style g' less, degree of branching is higher)
Embodiment
Embodiment 1
By vinylbenzene (10.4021g, 0.1mol), the own ester (0.0511g of methacrylic acid-3-sulfydryl, 0.25mmol) and Diisopropyl azodicarboxylate (AIBN, 0.1104g, 0.67mmol) dissolve after mixing and join in the aqueous solution of the 50g polyvinyl alcohol that concentration expressed in percentage by weight is 0.24%, nitrogen bubble is got rid of oxygen, under the stirring velocity of 300 r/min, controlling polymeric reaction temperature is 85 ℃, polyreaction 5 hours, polymer yield is 82%, and obtaining diameter is the granules of polystyrene of 2mm left and right.Adopt three detection gel permeation chromatographs to be analyzed polymkeric substance, result is as follows: the scattering of light weight-average molecular weight
M W.MALLS=293300, molecular weight distribution PDI=6.30, Mark-Houwink index α=0.628, branching factor g '=0.78, confirm that resulting polymers has branched structure.The limiting viscosity that Fig. 1 is embodiment 1 gained branched polystyrene and linear polystyrene thing is with the change of molecular weight figure.The branching factor that Fig. 4 is embodiment 1 gained branched polymer
g' with the variation diagram of molecular weight.(
g' be limiting viscosity (Intrinsic Viscosity) ratio of branched polymer and simple linear polymer under the same molecular amount
g'=IV
Branching / IV
Line style g' less, degree of branching is higher).
Embodiment 2
By vinylbenzene (10.4044g, 0.1mol), own ester (the 0.1021g of methacrylic acid-3-sulfydryl, 0.5mmol) and Diisopropyl azodicarboxylate (AIBN, 0.0821g, 0.5mmol) dissolve after mixing and join in the aqueous solution of the 100g polyvinyl alcohol that concentration expressed in percentage by weight is 0.3%, nitrogen bubble is got rid of oxygen, under the stirring velocity of 350 r/min, controlling polymeric reaction temperature is 85 ℃, polyreaction 4 hours, again polymeric reaction temperature is brought up to 90 ℃ of strengthening reactions 1 hour, polymer yield is 89%, obtaining diameter is the granules of polystyrene of 0.5mm left and right.Adopt three detection gel permeation chromatographs to be analyzed polymkeric substance, result is as follows: the scattering of light weight-average molecular weight
M W.MALLS=805000, molecular weight distribution PDI=7.23, Mark-Houwink index α=0.677, branching factor g '=0.53, confirm that resulting polymers has branched structure.The limiting viscosity that Fig. 1 is embodiment 2 gained branched polystyrenes and linear polystyrene thing is with the change of molecular weight figure.
Embodiment 3
By vinylbenzene (10.4037g, 0.1mol), the own ester (0.4083g of methacrylic acid-3-sulfydryl, 2mmol) and Diisopropyl azodicarboxylate (AIBN, 0.4925g, 3mmol) dissolving joins in the aqueous solution of the 50g polyvinyl alcohol that concentration expressed in percentage by weight is 0.3% after mixing, nitrogen bubble is got rid of oxygen, under the stirring velocity of 500 r/min, controlling polymeric reaction temperature is 85 ℃, polyreaction 4 hours, polymeric reaction temperature is brought up to 90 ℃ of strengthening reactions 1 hour, polymer yield is 85% again, and obtaining diameter is the granules of polystyrene of 1mm left and right.Adopt three detection gel permeation chromatographs to be analyzed polymkeric substance, result is as follows: the scattering of light weight-average molecular weight
M W.MALLS=731900, molecular weight distribution PDI=7.87, Mark-Houwink index α=0.610, branching factor g '=0.59, confirm that resulting polymers has branched structure.
Embodiment 4
By vinylbenzene (10.4111g, 0.1mol), methacrylic acid sulfydryl propionyloxy ethyl ester (0.1093g, 0.5mmol) and Diisopropyl azodicarboxylate (AIBN, 0.0825g, 0.5mmol) dissolve after mixing and join in the aqueous solution of the 100g polyvinyl alcohol that concentration expressed in percentage by weight is 0.3%, nitrogen bubble is got rid of oxygen, under the stirring velocity of 350 r/min, controlling polymeric reaction temperature is 85 ℃, polyreaction 4 hours, again polymeric reaction temperature is brought up to 90 ℃ of strengthening reactions 1 hour, polymer yield is 86%, obtaining diameter is the poly methyl methacrylate particle of 0.5mm left and right.Adopt three detection gel permeation chromatographs to be analyzed polymkeric substance, result is as follows: the scattering of light weight-average molecular weight
M W.MALLS=795600, molecular weight distribution PDI=6.96, Mark-Houwink index α=0.667, branching factor g '=0.68, confirm that resulting polymers has branched structure.The limiting viscosity that Fig. 1 is embodiment 4 gained branched polystyrenes and linear polystyrene thing is with the change of molecular weight figure.
Embodiment 5
By methyl methacrylate (10.0211g, 0.1mol), own ester (the 0.1020g of methacrylic acid-3-sulfydryl, 0.5mmol) and Diisopropyl azodicarboxylate (AIBN, 0.0823g, 0.5mmol) dissolve after mixing and join in the aqueous solution of the 100g polyvinyl alcohol that concentration expressed in percentage by weight is 0.3%, nitrogen bubble is got rid of oxygen, under the stirring velocity of 350 r/min, controlling polymeric reaction temperature is 75 ℃, polyreaction 2 hours, again polymeric reaction temperature is brought up to 80 ℃ of strengthening reactions 0.5 hour, polymer yield is 80%, obtaining diameter is the poly methyl methacrylate particle of 0.5mm left and right.Adopt three detection gel permeation chromatographs to be analyzed polymkeric substance, result is as follows: the scattering of light weight-average molecular weight
M W.MALLS=1061000, molecular weight distribution PDI=6.65, Mark-Houwink index α=0.646, branching factor g '=0.40, confirm that resulting polymers has branched structure.The limiting viscosity that Fig. 2 is embodiment 5 gained branching polymethylmethacrylates and Linear Polymethyl methacrylate is with the change of molecular weight figure.The branching factor that Fig. 4 is embodiment 5 gained branched polymers
g' with the variation diagram of molecular weight.
Embodiment 6
By methyl acrylate (8.6112g, 0.1mol), methacrylic acid sulfydryl propionyloxy ethyl ester (0.1089g, 0.5mmol) and Diisopropyl azodicarboxylate (AIBN, 0.0820g, 0.5mmol) dissolve after mixing and join in the aqueous solution of the 86g polyvinyl alcohol that concentration expressed in percentage by weight is 0.35%, nitrogen bubble is got rid of oxygen, under the stirring velocity of 350 r/min, controlling polymeric reaction temperature is 70 ℃, polyreaction 2 hours, again polymeric reaction temperature is brought up to 80 ℃ of strengthening reactions 0.5 hour, polymer yield is 82%, obtaining diameter is the polymethyl acrylate particle of 0.5mm left and right.Adopt three detection gel permeation chromatographs to be analyzed polymkeric substance, result is as follows: the scattering of light weight-average molecular weight
M W.MALLS=422100, molecular weight distribution PDI=6.64, Mark-Houwink index α=0.610, branching factor g '=0.53, confirm that resulting polymers has branched structure.The branching factor that Fig. 4 is embodiment 6 gained branched polymers
g' with the variation diagram of molecular weight.
Embodiment 7
By vinyl acetate (8.6091g, 0.1mol), own ester (the 0.1023g of methacrylic acid-3-sulfydryl, 0.5mmol) and Diisopropyl azodicarboxylate (AIBN, 0.0821g, 0.5mmol) dissolve after mixing and join in the aqueous solution of the 86g polyvinyl alcohol that concentration expressed in percentage by weight is 0.35%, nitrogen bubble is got rid of oxygen, under the stirring velocity of 350 r/min, controlling polymeric reaction temperature is 65 ℃, polyreaction 2 hours, again polymeric reaction temperature is brought up to 75 ℃ of strengthening reactions 1 hour, polymer yield is 70%, obtaining diameter is the polyvinyl acetate (PVA) particle of 0.5mm left and right.Adopt three detection gel permeation chromatographs to be analyzed polymkeric substance, result is as follows: the scattering of light weight-average molecular weight
M W.MALLS=551500, molecular weight distribution PDI=6.79, Mark-Houwink index α=0.562, branching factor g '=0.66, confirm that resulting polymers has branched structure.The limiting viscosity that Fig. 3 is embodiment 7 gained branching polyvinyl acetate (PVA) and line style polyvinyl acetate (PVA) is with the change of molecular weight figure.The branching factor that Fig. 4 is embodiment 7 gained branched polymers
g' with the variation diagram of molecular weight.
Embodiment 8
By vinylbenzene (5.2011g, 0.05mol), methyl methacrylate (5.0091g, 0.05mol), own ester (the 0.0511g of methacrylic acid-3-sulfydryl, 0.25mmol) and Diisopropyl azodicarboxylate (AIBN, 0.0823g, 0.5mmol) dissolve after mixing and join in the aqueous solution of the 100g polyvinyl alcohol that concentration expressed in percentage by weight is 0.3%, nitrogen bubble is got rid of oxygen, under the stirring velocity of 350 r/min, controlling polymeric reaction temperature is 75 ℃, polyreaction 10 hours, again polymeric reaction temperature is brought up to 85 ℃ of strengthening reactions 2 hours, polymer yield is 80%, obtaining diameter is polystyrene and the methylmethacrylate copolymer particle of 0.5mm left and right.Adopt three detection gel permeation chromatographs to be analyzed polymkeric substance, result is as follows: the scattering of light weight-average molecular weight
M W.MALLS=522900, molecular weight distribution PDI=5.35, Mark-Houwink index α=0.702, branching factor g '=0.69, confirm that resulting polymers has branched structure.The branching factor that Fig. 4 is embodiment 8 gained branched polymers
g' with the variation diagram of molecular weight.
Claims (4)
1. suspension polymerization prepares the method for branched polymer, it is characterized in that carrying out according to following step: adopting the function monomer that contains polymerizable double bond and chain transfer sulfydryl is branched monomer, take polyvinyl alcohol water solution as dispersion agent, Diisopropyl azodicarboxylate is initiator, carry out suspension polymerization and obtain the uniform branched polymer microballoon of particle diameter under the stirring velocity of setting and polymerization temperature, stirring velocity is 300 ~ 500r/min, polymeric reaction temperature is controlled at 65 ~ 90 ℃, and polymerization reaction time is controlled as 3-12 hour.
2. suspension polymerization according to claim 1 prepares the method for branched polymer, it is characterized in that wherein said branched monomer: initiator: the mol ratio of polymerization single polymerization monomer is 0.25 ~ 2:0.5 ~ 3:100, water in wherein said polyvinyl alcohol water solution: the mass ratio of polymerization single polymerization monomer is 5 ~ 10:1, and the weight percent of the polyvinyl alcohol in wherein said polyethylene of dispersing agent alcohol solution is 0.24% ~ 0.35%.
3. suspension polymerization according to claim 1 prepares the method for branched polymer, it is characterized in that wherein said branched monomer is methacrylic acid-own ester of 3-sulfydryl or methacrylic acid sulfydryl propionyloxy ethyl ester.
4. suspension polymerization according to claim 1 prepares the method for branched polymer, it is characterized in that wherein said polymerization single polymerization monomer vinylbenzene, (methyl) acrylate or vinyl acetate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103319640A (en) * | 2013-06-07 | 2013-09-25 | 常州大学 | Preparation method of styrene-acrylic resin with high solid content |
| CN104313796A (en) * | 2014-09-09 | 2015-01-28 | 天津工业大学 | Manufacturing method for fibrous membrane for oil-water separation |
| CN106632789A (en) * | 2016-12-30 | 2017-05-10 | 常州大学 | Method for preparing branched polystyrene at room temperature by means of emulsion polymerization |
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| CN101891858A (en) * | 2010-03-04 | 2010-11-24 | 江苏工业学院 | Method for preparing branched polymer by conventional free radical polymerization |
| CN101260162B (en) * | 2008-04-18 | 2011-04-20 | 成都博深高技术材料开发有限公司 | Reactivity high-branching vinyl polymer and preparation method |
| CN102108108A (en) * | 2011-01-05 | 2011-06-29 | 常州大学 | Method for synthesizing branched polymer by using vinyl benzyl sulfydryl propionate as a functional monomer |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101260162B (en) * | 2008-04-18 | 2011-04-20 | 成都博深高技术材料开发有限公司 | Reactivity high-branching vinyl polymer and preparation method |
| CN101891858A (en) * | 2010-03-04 | 2010-11-24 | 江苏工业学院 | Method for preparing branched polymer by conventional free radical polymerization |
| CN102108108A (en) * | 2011-01-05 | 2011-06-29 | 常州大学 | Method for synthesizing branched polymer by using vinyl benzyl sulfydryl propionate as a functional monomer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319640A (en) * | 2013-06-07 | 2013-09-25 | 常州大学 | Preparation method of styrene-acrylic resin with high solid content |
| CN103319640B (en) * | 2013-06-07 | 2015-12-23 | 常州大学 | A kind of preparation method of styrene-acrylic resin with high solid content |
| CN104313796A (en) * | 2014-09-09 | 2015-01-28 | 天津工业大学 | Manufacturing method for fibrous membrane for oil-water separation |
| CN106632789A (en) * | 2016-12-30 | 2017-05-10 | 常州大学 | Method for preparing branched polystyrene at room temperature by means of emulsion polymerization |
| CN106632789B (en) * | 2016-12-30 | 2019-05-28 | 常州大学 | The method that emulsion polymerization room temperature prepares branched polystyrene |
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Application publication date: 20130220 |