CN103319668A - Preparation method of butyl methacrylate-dimethylaminoethyl methacrylate block copolymer - Google Patents
Preparation method of butyl methacrylate-dimethylaminoethyl methacrylate block copolymer Download PDFInfo
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- CN103319668A CN103319668A CN2013102566743A CN201310256674A CN103319668A CN 103319668 A CN103319668 A CN 103319668A CN 2013102566743 A CN2013102566743 A CN 2013102566743A CN 201310256674 A CN201310256674 A CN 201310256674A CN 103319668 A CN103319668 A CN 103319668A
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Abstract
The invention relates to a preparation method of a butyl methacrylate-dimethylaminoethyl methacrylate block copolymer. A polybutyl methacrylate precursor is obtained through a reaction among a reaction system monomer BMA (butyl methacrylate), an initiator AIBN, a molecular weight regulator 1,1-diphenylethlene and a solvent; the polybutyl methacrylate precursor is used as an initiator of the dimethylaminoethyl methacrylate reaction; and the butyl methacrylate-dimethylaminoethyl methacrylate block copolymer is obtained by heating polymerization. Compared with the butyl methacrylate-dimethylaminoethyl methacrylate block copolymer prepared by an ATRP (atom transfer radical polymerization) method, the preparation method of a butyl methacrylate-dimethylaminoethyl methacrylate block copolymer, provided by the invention, has the advantages of simple reaction conditions, easiness in operation, low production cost and no residue of inorganic catalyst, is favorable for industrial production, and has a broad application prospect in the field of coating dispersants.
Description
Technical field
The present invention relates to technical field of polymer chemistry, especially relate to the preparation method of a kind of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer.
Background technology
Amphipathic nature block polymer refers to the multipolymer that is comprised of hydrophilic and oleophylic section.Amphipathic nature polyalcohol becomes one of focus of current polymer subject area research owing to having special character, this base polymer forms take hydrophilic section as shell in water, hydrophobic section is the micellar structure of nuclear, in organic solvent, then form " reverse micelle " of inverted configuration, studies show that, micella also may be by further assembling the aggregate that forms compound with regular structure.Amphipathic nature block polymer can promote the mixing of water and oil phase, and at tensio-active agent, the dispersion agent field is widely used.
At present, the method for the comparatively perfect synthetic segmented copolymer of development is anionoid polymerization.It is synthesis of narrow molecular weight distribution and block, the most important a kind of polymerization process of unique construction polymer such as star-like.But anionoid polymerization is easily by the trace impurity in system inhibition, and polymerizing condition is harsh, has the monomer of active group such as hydroxyl, amido also inapplicable for some.
Butyl methacrylate is a kind of common oiliness monomer, and its glass transition temperature of polymer is widely used at coating and adhesive area near room temperature.Dimethylaminoethyl methacrylate (DMAEMA) is a kind of broad-spectrum functional monomer, and it has the characteristic of alkene, amine, ester compound simultaneously, and the chemical reactions such as polymerization, addition, quaternary ammoniated and hydrolysis can occur under certain condition.The segmented copolymer of butyl methacrylate-dimethylaminoethyl methacrylate has wide practical use in the coating dispersant field.
Owing to the impact of the amino in the dimethylaminoethyl methacrylate, can not obtain the segmented copolymer (PBMA-g-PDMAEMA) of butyl methacrylate-dimethylaminoethyl methacrylate by anionoid polymerization.Compare with other polyreaction types, the polymerisable monomeric species of Transfer Radical Polymerization (ATRP) is many, easy to control.The people such as Mao carry out the atom transfer radical polymerization of DMAEMA under 25 ℃ take CuCl/HMTETA as initiator system, obtain controlled PDMAEMA macromole evocating agent [the Mao B. of molecular weight and molecular weight, Gan L., Gan Y., Li X., Ravi P., Tam K..J Polym Sci Part A Polym Chem2004; 42:5161-9.].Macromole evocating agent PDMAEMA further causes the atom transfer radical polymerization of the second monomer butyl methacrylate (BMA), and then obtain amphipathic nature block polymer PDMAEMA-b-PBMA[Leena N., Susanna H., Janne L..Ultra-thin films of cationic amphiphilic poly (2-(dimethylamino) ethyl methacrylate) based block copolymers as surface wettability modifiers Polymer2009; 50:5250-5261.].But the catalyzer that uses in the middle of the ATRP method is generally the transition metal salt, and large usage quantity, poisonous and color are difficult to remove, and the used part of polymerization is also comparatively expensive, is unfavorable for suitability for industrialized production.The polymer ends that while ATRP obtains inevitably can be with the lower carbon of chemical bond energy-bromine key end group, and this will have influence on the heat-resisting and ageing-resistant performance of the finished product.
Summary of the invention
The technical problem to be solved in the present invention is: prepare the problem that catalyst levels is large, cost is high, resulting polymers has catalyst residue in the PBMA-b-PDMAEMA process in order to overcome ATRP in the prior art, a kind of method for preparing butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer is provided.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of a kind of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer may further comprise the steps:
1) preparation of poly-n-butyl methacrylate: with monomers B MA, initiator A IBN, molecular weight regulator 1,1-diphenylethlene and solvent join in the reactor and stir, repeatedly vacuumize and logical argon gas to remove oxygen and moisture, then be heated under 70-75 ℃ the condition and react 20-25h.
The mol ratio of described BMA and AIBN is 100:0.4-1.5, and the mol ratio of described AIBN and 1，1-diphenylethylene is 1:2, and described solvent is a kind of in toluene, the butylacetate;
2) purification of poly-n-butyl methacrylate: after reaction is finished, product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive methyl alcohol and precipitates, filter, the throw out that obtains is joined fully dissolving in the trichloromethane, then, the throw out chloroform soln splashed in the excessive methanol precipitate, repeat 2-3 time to remove unreacted BMA, AIBN, 1，1-diphenylethylene and a small amount of solvent are at last with the throw out vacuum-drying that obtains, namely obtain poly-n-butyl methacrylate, structure is as follows:
3) preparation of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: with step 2) PBMA of gained is dissolved in the butylacetate, again the second monomer DMAEMA is joined in the butylacetate that is dissolved with PBMA, repeatedly vacuumize after stirring and logical argon gas to remove oxygen and moisture, then be heated under 85 ℃ the condition and react 4-6h.
Wherein, the mass ratio of described PBMA and DMAEMA is 1:0.5-5.
4) purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction is finished, product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 2-3 time to remove unreacted PBMA and a small amount of solvent, with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer afterwards, structure is as follows:
Particularly, described type of heating is the oil bath heating.
The invention has the beneficial effects as follows: the preparation method of a kind of butyl methacrylate provided by the invention-dimethylaminoethyl methacrylate segmented copolymer, compare with the butyl methacrylate of using the preparation of ATRP method-dimethylaminoethyl methacrylate segmented copolymer, reaction conditions is simple, easy handling, production cost are low, there be not the residual of organic catalyst, be conducive to suitability for industrialized production, can effectively solve the reduction that causes the heat-resisting and ageing-resistant performance of product owing to organic catalyst is residual.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is the nuclear magnetic spectrogram of the butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer of embodiment 3 gained;
Fig. 2 is poly-n-butyl methacrylate and the gpc analysis that gathers (butyl methacrylate-b-dimethylaminoethyl methacrylate) among the embodiment 3.
Embodiment
Below in conjunction with specific embodiment, further the present invention is set forth, should be understood that quoting embodiment only is used for explanation the present invention, limits the scope of the invention and be not used in.
Embodiment 1
(1) polymerization formula: the mol ratio of monomer (BMA), initiator (AIBN), 1，1-diphenylethylene is 100:0.4:0.8, adds to equal the toluene of total mass 50% as solvent again.
Polymerization procedure: in the 250mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add BMA monomer 50g(0.35mol), initiator A IBN0.2310g(0.0014mol), 1,1-diphenylethlene 0.5070g(0.0028mol), solvent toluene 50g, mix, system is vacuumized logical argon gas three times repeatedly, at 70 ℃ of lower reaction 25h.
The purification of poly-n-butyl methacrylate: after reaction finishes, remove solvent in the system through rotary evaporation, until till liquid no longer drips in the rotatory evaporator, obtain the product of the little thickness of water white transparency.To revolve product after the steaming splashes in the excessive methyl alcohol and precipitates, filter, the throw out that obtains is joined in the trichloromethane fully dissolving, then, the throw out chloroform soln splashed in the excessive methanol precipitate, repeat 2 times to remove unreacted BMA, AIBN, 1,1-diphenylethlene and a small amount of solvent with the throw out vacuum-drying that obtains, namely obtain poly-n-butyl methacrylate at last, product quality is 33.88g, and gas phase tracking report transformation rate is 67.76%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=26400 of PBMA, PDI=1.58.
(2) polymerization formula: PBMA synthetic in the step (1) is as macromole evocating agent, and the mass ratio of PBMA and DMAEMA is 1:1, add again equal total amount 50% butylacetate as solvent.
Polymerization procedure: in the 100mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add PBMA10g, monomer DMAEMA10g, solvent acetic acid butyl ester 20g mixes, system is vacuumized logical argon gas three times repeatedly to remove oxygen and moisture, at 85 ℃ of lower reaction 5h.
The purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction finishes, remove solvent in the system through rotary evaporation, obtain the product of water white transparency thickness.Product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 2 times to remove unreacted PBMA and a small amount of solvent, afterwards with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer, product quality is 4.51g, and gas phase tracking report transformation rate is 49.31%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=49800 of PBMA-b-PDMAEMA, PDI=1.70.
Synthetic PBMA is as macromole evocating agent in embodiment 1 step (1), and the mass ratio of PBMA and DMAEMA is 1:5, and adding equals 50% butylacetate of total amount as solvent again.
Polymerization procedure: in the 100mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add PBMA10g, monomer DMAEMA50g, solvent acetic acid butyl ester 20g mixes, system is vacuumized logical argon gas three times repeatedly to remove oxygen and moisture, at 85 ℃ of lower reaction 6h.
The purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction finishes, remove solvent in the system through rotary evaporation, obtain the product of water white transparency thickness.Product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 2 times to remove unreacted PBMA and a small amount of solvent, afterwards with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer, product quality is 19.62g, and gas phase tracking report transformation rate is 42.44%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=60200 of PBMA-b-PDMAEMA, PDI=2.36.
Embodiment 3
(1) polymerization formula: the mol ratio of monomer (BMA), initiator (AIBN), 1，1-diphenylethylene is 100:1:2, adds to equal the butylacetate of total mass 50% as solvent again.
Polymerization procedure: in the 250mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add BMA monomer 50g(0.35mol), initiator A IBN0.2310g(0.0035mol), DPE0.5070g(0.0070mol), solvent toluene 50g, mix, at 75 ℃ of lower reaction 20h.
The purification of poly-n-butyl methacrylate: after reaction finishes, remove solvent in the system through rotary evaporation, until till liquid no longer drips in the rotatory evaporator, obtain the product of the little thickness of water white transparency.To revolve product after the steaming splashes in the excessive methyl alcohol and precipitates, filter, the throw out that obtains is joined in the trichloromethane fully dissolving, then, the throw out chloroform soln splashed in the excessive methanol precipitate, repeat 3 times to remove unreacted BMA, AIBN, 1,1-diphenylethlene and a small amount of solvent with the throw out vacuum-drying that obtains, namely obtain poly-n-butyl methacrylate at last, product quality is 31.52g, and gas phase tracking report transformation rate is 63.04%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=15100 of PBMA, PDI=1.43.
(2) polymerization formula: PBMA synthetic in the step (1) is as macromole evocating agent, and the mass ratio of PBMA and DMAEMA is 1:0.5, add again equal total amount 50% butylacetate as solvent.
Polymerization procedure: in the 100mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add PBMA10g, monomer DMAEMA5g, solvent acetic acid butyl ester 15g mixes, system is vacuumized logical argon gas three times repeatedly to remove oxygen and moisture, at 85 ℃ of lower reaction 5.5h.
The purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction finishes, remove solvent in the system through rotary evaporation, obtain the product of water white transparency thickness.Product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 2 times to remove unreacted PBMA and a small amount of solvent, afterwards with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer, product quality is 2.56g, and gas phase tracking report transformation rate is 50.35%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=25600 of PBMA-b-PDMAEMA, PDI=1.35.
Synthetic PBMA is as macromole evocating agent in embodiment 3 steps (1), and the mass ratio of PBMA and DMAEMA is 1:1, and adding equals 50% butylacetate of total amount as solvent again.
Polymerization procedure: in the 100mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add PBMA10g, monomer DMAEMA10g, solvent acetic acid butyl ester 20g mixes, system is vacuumized logical argon gas three times repeatedly to remove oxygen and moisture, at 85 ℃ of lower reaction 4h.
The purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction finishes, remove solvent in the system through rotary evaporation, obtain the product of water white transparency thickness.Product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 3 times to remove unreacted PBMA and a small amount of solvent, afterwards with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer, product quality is 5.96g, and gas phase tracking report transformation rate is 64.29%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=39000 of PBMA-b-PDMAEMA, PDI=1.69.
Embodiment 5
Synthetic PBMA is as macromole evocating agent in embodiment 3 steps (1), and the mass ratio of PBMA and DMAEMA is 1:3, and adding equals 50% butylacetate of total amount as solvent again.
Polymerization procedure: in the 250mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add PBMA10g, monomer DMAEMA30g, solvent acetic acid butyl ester 40g mixes, system is vacuumized logical argon gas three times repeatedly to remove oxygen and moisture, at 85 ℃ of lower reaction 4.5h.
The purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction finishes, remove solvent in the system through rotary evaporation, obtain the product of water white transparency thickness.Product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 3 times to remove unreacted PBMA and a small amount of solvent, afterwards with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer, product quality is 12.16g, and gas phase tracking report transformation rate is 50.20%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=43200 of PBMA-b-PDMAEMA, PDI=1.9.
Embodiment 6
Synthetic PBMA is as macromole evocating agent in embodiment 3 steps (1), and the mass ratio of PBMA and DMAEMA is 1:5, and adding equals 50% butylacetate of total amount as solvent again.
Polymerization procedure: in the 250mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add PBMA10g, monomer DMAEMA50g, solvent acetic acid butyl ester 60g mixes, system is vacuumized logical argon gas three times repeatedly to remove oxygen and moisture, at 85 ℃ of lower reaction 5h.
The purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction finishes, remove solvent in the system through rotary evaporation, obtain the product of water white transparency thickness.Product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 3 times to remove unreacted PBMA and a small amount of solvent, afterwards with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer, product quality is 16.56g, and gas phase tracking report transformation rate is 46.50%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=53700 of PBMA-b-PDMAEMA, PDI=1.91.
Embodiment 7
(1) polymerization formula: the mol ratio of monomer (BMA), initiator (AIBN), 1，1-diphenylethylene is 100:1.5:3, adds to equal the toluene of total mass 50% as solvent again.
Polymerization procedure: in the 250mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add BMA monomer 50g(0.35mol), initiator A IBN0.8662g(0.0053mol), DPE1.9014g(0.0105mol), solvent toluene 50g, mix, system is vacuumized logical argon gas three times repeatedly to remove oxygen and moisture, at 70 ℃ of lower reaction 25h.
The purification of poly-n-butyl methacrylate: after reaction finishes, remove solvent in the system through rotary evaporation, until till liquid no longer drips in the rotatory evaporator, obtain the product of the little thickness of water white transparency.To revolve product after the steaming splashes in the excessive methyl alcohol and precipitates, filter, the throw out that obtains is joined in the trichloromethane fully dissolving, then, the throw out chloroform soln splashed in the excessive methanol precipitate, repeat 3 times to remove unreacted BMA, AIBN, 1,1-diphenylethlene and a small amount of solvent with the throw out vacuum-drying that obtains, namely obtain poly-n-butyl methacrylate at last, product quality is 36.02g, and gas phase tracking report transformation rate is 72.05%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=9200 of PBMA, PDI=1.67.
(2) polymerization formula: PBMA synthetic in the step (1) is as macromole evocating agent, and the mass ratio of PBMA and DMAEMA is 1:1, add again equal total amount 50% butylacetate as solvent.
Polymerization procedure: in the 100mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add PBMA10g, monomer DMAEMA10g, solvent acetic acid butyl ester 20g mixes, system is vacuumized logical argon gas three times repeatedly to remove oxygen and moisture, at 85 ℃ of lower reaction 6h.In an embodiment should there be the particularly reaction times
The purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction finishes, remove solvent in the system through rotary evaporation, obtain the product of water white transparency thickness.Product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 2 times to remove unreacted PBMA and a small amount of solvent, afterwards with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer, product quality is 4.79g, and gas phase tracking report transformation rate is 47.91%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=35300 of PBMA-b-PDMAEMA, PDI=1.59.
Synthetic PBMA is as macromole evocating agent in embodiment 7 steps (1), and the mass ratio of PBMA and DMAEMA is 1:5, and adding equals 50% butylacetate of total amount as solvent again.
Polymerization procedure: in the 250mL four-hole boiling flask of thermometer, magnetic stir bar is housed, add PBMA10g, monomer DMAEMA50g, solvent acetic acid butyl ester 60g mixes, system is vacuumized logical argon gas three times repeatedly to remove oxygen and moisture, at 85 ℃ of lower reaction 6h.
The purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction finishes, remove solvent in the system through rotary evaporation, obtain the product of water white transparency thickness.Product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 3 times to remove unreacted PBMA and a small amount of solvent, afterwards with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer, product quality is 18.95g, and gas phase tracking report transformation rate is 40.96%.Final product is carried out gel permeation chromatography (GPC) test, obtain the number-average molecular weight Mn=53300 of PBMA-b-PDMAEMA, PDI=2.25.
Take above-mentioned foundation desirable embodiment of the present invention as enlightenment, by above-mentioned description, the relevant staff can in the scope that does not depart from this invention technological thought, carry out various change and modification fully.The technical scope of this invention is not limited to the content on the specification sheets, must determine its technical scope according to the claim scope.
Claims (2)
1. the preparation method of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer is characterized in that may further comprise the steps:
1) preparation of poly-n-butyl methacrylate: with monomers B MA, initiator A IBN, molecular weight regulator 1,1-diphenylethlene and solvent join in the reactor and stir, repeatedly vacuumize and logical argon gas to remove oxygen and moisture, then be heated under 70-75 ℃ the condition and react 20-25h;
The mol ratio of described BMA and AIBN is 100:0.4-1.5, and the mol ratio of described AIBN and 1，1-diphenylethylene is 1:2, and described solvent is a kind of in toluene, the butylacetate;
2) purification of poly-n-butyl methacrylate: after reaction is finished, product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive methyl alcohol and precipitates, filter, the throw out that obtains is joined fully dissolving in the trichloromethane, then, the throw out chloroform soln splashed in the excessive methanol precipitate, repeat 2-3 time to remove unreacted BMA, AIBN, 1，1-diphenylethylene and a small amount of solvent are at last with the throw out vacuum-drying that obtains, namely obtain poly-n-butyl methacrylate, structure is as follows:
3) preparation of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: with step 2) PBMA of gained is dissolved in the butylacetate, again the second monomer DMAEMA is joined in the butylacetate that is dissolved with PBMA, repeatedly vacuumize after stirring and logical argon gas to remove oxygen and moisture, then be heated under 85 ℃ the condition and react 4-6h;
Wherein, the mass ratio of described PBMA and DMAEMA is 1:0.5-5;
4) purification of butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer: after reaction is finished, product is revolved steaming with desolventizing in rotatory evaporator, until till liquid no longer drips in the rotatory evaporator, to revolve product after the steaming splashes in the excessive sherwood oil and precipitates, filter, the throw out that obtains is joined fully dissolving among the THF, then, sedimentary THF solution splashed in the excessive sherwood oil precipitate, repeat 2-3 time to remove unreacted PBMA and a small amount of solvent, with throw out vacuum-drying, namely obtain butyl methacrylate-dimethylaminoethyl methacrylate segmented copolymer afterwards, structure is as follows:
2. the preparation method of a kind of butyl methacrylate as claimed in claim 1-dimethylaminoethyl methacrylate segmented copolymer is characterized in that: described type of heating is the oil bath heating.
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| CN104650306A (en) * | 2015-01-14 | 2015-05-27 | 中科院广州化学有限公司 | Acrylate-acrylamide type block polymer, synthetic method and application thereof |
| CN104650306B (en) * | 2015-01-14 | 2017-06-23 | 中科院广州化学有限公司 | Acrylate acrylamide kind block polymer and its synthetic method and application |
| CN108102489A (en) * | 2017-12-16 | 2018-06-01 | 长沙无道工业设计有限公司 | A kind of Environmental Protective Water-paint and preparation method thereof |
| CN114891385A (en) * | 2022-05-16 | 2022-08-12 | 天津大学 | Ag-Ag 2 S double-sided particles, amphiphilic antifouling coating and preparation method thereof |
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