CN101544722A - Method for preparing methyl methacrylate-acrylic acid block polymer with the existence of 1, 1-diphenylethylene - Google Patents
Method for preparing methyl methacrylate-acrylic acid block polymer with the existence of 1, 1-diphenylethylene Download PDFInfo
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- CN101544722A CN101544722A CN200810102890A CN200810102890A CN101544722A CN 101544722 A CN101544722 A CN 101544722A CN 200810102890 A CN200810102890 A CN 200810102890A CN 200810102890 A CN200810102890 A CN 200810102890A CN 101544722 A CN101544722 A CN 101544722A
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Abstract
The invention relates to a method for preparing methyl methacrylate-acrylic acid block polymer with the existence of 1, 1-diphenylethylene, which belongs to the field of high polymer chemistry. The invention solves the problems of complex polymerization systems, severe reaction conditions, fussy operation steps and inconvenience for industrial production in the prior PMMA-b-PAA preparation method. The method comprises the following steps: free radicals of MMA are polymerized to prepare a PMMA precursor with a special semiquinone structure and controllable molecular weight by taking AIBN as an evocating agent with the existence of little DPE; the polymerization of acrylic acid monomer is directly carried out with the existence of PMMA; and the polymerization systems are separated to obtain a PMMA-b-PAA amphipathic block polymer. The invention has the advantages of simple components of the DPE polymerization system, and same reaction conditions with common free radical polymerization and simple operation steps, directly carries out the polymerization of AA monomers, avoids the hydration to polyacrylic acid tert-butyl ester chain segment and is more beneficial to industrial production.
Description
Technical field
The invention belongs to chemical field, particularly the composition of C08L macromolecular compound relates in particular to a kind of 1 (DPE) and has the method for preparing block polymer down.
Background technology
Methyl methacrylate-vinylformic acid Amphipathilic block polymer (PMMA-b-PAA) is a weak polyelectrolyte because of its hydrophilic section polyacrylic acid, degree of ionization can make it have a wide range of applications in fields such as medicament slow releases by pH value and solution ion strength control.Its basic preparation method adopts the living polymerization substep charging process of radical protection monomer tert-butyl acrylate (tBA): people such as Teyssi é are solvent with the tetrahydrofuran (THF), with the reinforced method of substep, under-78 ℃ of conditions, carry out the active anionic polymerization of monomers methyl methacrylate (MMA) and tBA, thereby obtain the block polymer PMMA-b-P tBA of MMA and tBA; And in the presence of p-methyl benzenesulfonic acid, be that the further hydrolysis of solvent promptly can obtain Amphipathilic block polymer PMMA-b-PAA[Varshney SK with toluene with gained PMMA-b-P tBA, Jacobs C, Hautekeer JP, Bayard P, Jerome R, Fayt R, Teyssi é P, Macromolecules, 24,4997, (1991)].People such as Ma are initiator system carries out tBA under 50 ℃ of conditions atom transfer radical polymerization (ATRP) with CuBr/PMDETA, obtain the controlled PtBA macromole evocating agent of molecular weight, the PtBA macromole evocating agent can further cause the second monomeric atom transfer radical polymerization, and then PMA-b-P tBA and P tBA-b-PMA-b-PS have been obtained, is that solvent further hydrolysis promptly can obtain Amphipathilic block polymer PMA-b-PAA and PAA-b-PMA-b-PS[Ma Q with the methylene dichloride with gained PMA-b-P tBA and P tBA-b-PMA-b-PS in the presence of trifluoroacetic acid, Wooley KL, J.Polym.Sci., Part A:Polym.Chem., 38,4805, (2000)].But general living polymerisation process is as living anion polymerization, atom transfer radical polymerization etc., polymerization system more complicated, severe reaction conditions, complex operation step, and the hydrolysis of polyacrylic acid tert-butyl ester segment is relatively more difficult, has therefore limited its large-scale industrial production.
Polymerization system under DPE exists has advantages such as simple to operate, that reaction conditions is gentle, suitable monomers is extensive as a kind of novel activity/controllable free radical polymerization process, and identical with common radical polymerization on reaction conditions and the implementation method.It is initiator that people such as Bremser have described in international monopoly WO2002098933 in the presence of the DPE with ammonium persulphate (APS), do not add tensio-active agent or organic solvent, in water, cause the polymerization of mix monomer vinylformic acid (AA) and MMA, be dilute with water and add (methyl) acrylic ester monomer dispersions obtained, prepared solvent-free dispersion.People such as Nuyken have described the polymerization system in the presence of the DPE in European patent EP 1382619 and have prepared the block graft polymkeric substance.
But yet there are no the report that the polymerization system that utilizes under the DPE existence prepares methyl methacrylate-vinylformic acid block polymer.
Summary of the invention
The problem of purpose of the present invention in solving existing PMMA-b-PAA technology of preparing, and provide a kind of 1 to have the method for preparing methyl methacrylate-vinylformic acid block polymer down.
Method provided by the present invention may further comprise the steps:
1) preparation contains the controlled polymethylmethacrylate presoma of molecular weight of special semiquinone formula structure: with monomer M MA; initiator Diisopropyl azodicarboxylate (AIBN) and DPE add in the reaction vessel; in 70～90 ℃; at normal pressure; under the nitrogen protection atmosphere; carry out the MMA Raolical polymerizable; wherein, MMA and AIBN amount of substance are than being 100:0.8～0.4, and the ratio of AIBN and DPE amount of substance is 1:1.5～2; react after 3 hours; the polymerization system methanol extraction, filtration drying, resulting polymers dissolves again with trichloromethane; again behind methanol extraction; place vacuum drying oven 24h, obtain polymethylmethacrylate (PMMA) macromole presoma, structural formula is as follows:
2) preparation methyl methacrylate-vinylformic acid block polymer PMMA-b-PAA: gained PMMA presoma in monomer A A and the step 1) is dissolved in 1; in the 4-dioxane solvent; in 70～80 ℃; under normal pressure, nitrogen protection atmosphere, carry out the block polymerization reaction of monomer A A, 3～12 hours reaction times, wherein; the mass ratio of monomer A A and PMMA presoma is 5～1:1; reaction beginning post polymerization system becomes oyster white, and along with the polymerization system oyster white of carrying out of reaction is deepened, reaction equation is:
3) the polymerization reaction system cooling separation PMMA-b-PAA block polymer: with step 2), the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in ethyl acetate, remove remaining PMMA presoma, gained PMMA-b-PAA block polymer and PAA homopolymer are dispersed in the tetrahydrofuran (THF) (THF), the PMMA-b-PAA block polymer can self-assembly form stable micella in THF, and PAA (when molecular weight is higher) is insoluble to THF, remove PAA homopolymer precipitation, obtain the PMMA-b-PAA Amphipathilic block polymer.
Wherein, the MMA Raolical polymerizable temperature described in the step 1) is preferred 80 ℃; MMA and AIBN amount of substance are than preferred 100:0.6 in the MMA Raolical polymerizable; AIBN and DPE amount of substance are than preferred 1:2; Step 2) the preferred 5:1 of mass ratio of AA monomer and PMMA presoma in the polyreaction of the monomer A A described in.
Compared with prior art, the present invention has following beneficial effect:
The DPE of utilization polymerization system provided by the present invention prepares the method for PMMA-b-PAA block polymer, compare with other living polymerisation process, the DPE polymerization system is formed simple, reaction conditions is identical with common radical polymerization, and operation steps is simple, directly carry out the polymerization of Acrylic Acid Monomer, avoided the hydrolysis of polyacrylic acid tert-butyl ester segmental is more helped suitability for industrialized production.
Description of drawings
The PMMA-b-PAA block polymer that Fig. 1, embodiment 2 are prepared
1H NMR spectrogram.
The invention will be further described below in conjunction with the drawings and the specific embodiments.
Embodiment
1) with monomers methyl methacrylate (0.2 mole), the initiator Diisopropyl azodicarboxylate 196.8mg (1.2 mmole) and 1 of 20.0g, 1-diphenylethlene 324mg (1.8 mmole) joins in the single tap reaction flask that contains the magnetic agitation rotor, behind reaction 3h under 70 ℃ of conditions, stopped reaction also will precipitate in the reaction system impouring methyl alcohol, filtration drying, gained PMMA presoma is dissolved again with trichloromethane, methanol extraction is to remove unreacted monomer, initiator and 1, the 1-diphenylethlene, the resulting polymers powder is placed 24h at vacuum drying oven; It is 19% that weighting method records monomeric transformation efficiency, products therefrom molecular weight and molecular weight distribution: Mn=12900, PDI=1.45;
2) in containing single tap reaction flask of magnetic agitation rotor, add 0.5g PMMA presoma, 2.5g vinylformic acid and 20mL1, the 4-dioxane, mix the polymerization of under nitrogen protection, carrying out Acrylic Acid Monomer, 80 ℃ of temperature of reaction, reaction beginning post polymerization system becomes oyster white, along with the polymerization system oyster white of carrying out of reaction is deepened, in 6 hours reaction times, the Acrylic Acid Monomer transformation efficiency is 29%;
3) with step 2) in polymerization reaction system cooling, the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in a large amount of ethyl acetate, obtain PMMA presoma 0.10g, the mixture of separating obtained PMMA-b-PAA block polymer and PAA homopolymer is dispersed among the THF, separation does not obtain the explanation of PAA homopolymer does not have the PAA homopolymer to produce, and obtains PMMA-b-PAA Amphipathilic block polymer 1.12g.
1) with methyl methacrylate (0.2 mole), the catalyzer Diisopropyl azodicarboxylate 131.2mg (0.8 mmole) and 1 of 20.0g, 1-diphenylethlene 216mg (1.2 mmole) joins in the single tap reaction flask that contains the magnetic agitation rotor, under 80 ℃ of conditions, react 3h, stopped reaction also will precipitate in the reaction system impouring methyl alcohol, filtration drying, resulting PMMA presoma is dissolved again with trichloromethane, methanol extraction is to remove unreacted monomer, initiator and 1, the 1-diphenylethlene, the resulting polymers powder is placed 24h at vacuum drying oven.It is 22% that weighting method records monomeric transformation efficiency, product
1H NMR spectrogram is not seen impurity as shown in Figure 1.Molecular weight and molecular weight distribution gel permeation chromatography are standard specimen with the polystyrene of narrow distribution, gained result: Mn=13400, PDI=1.40.
2) in containing single tap reaction flask of magnetic agitation rotor, add 0.5g PMMA presoma; 2.5g vinylformic acid and 20mL1; the 4-dioxane; mix the polymerization of under nitrogen protection, carrying out Acrylic Acid Monomer; 80 ℃ of temperature of reaction; reaction beginning post polymerization system becomes oyster white, along with the polymerization system oyster white of carrying out of reaction is deepened.In 8 hours reaction times, monomer conversion is 35%;
3) polymerization reaction system is cooled off, the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in a large amount of ethyl acetate, obtain PMMA presoma 0.075g, the mixture of separating obtained PMMA-b-PAA block polymer and PAA homopolymer is dispersed among the THF, not isolating the explanation of PAA homopolymer does not have the PAA homopolymer to produce, and obtains PMMA-b-PAA Amphipathilic block polymer 1.30g.
1) with methyl methacrylate (0.2 mole), the catalyzer Diisopropyl azodicarboxylate 196.8mg (1.2 mmole) and 1 of 20.0g, 1-diphenylethlene 324mg (1.8 mmole) joins in the single tap reaction flask that contains the magnetic agitation rotor, under 80 ℃ of conditions, react 3h, stopped reaction also will precipitate in the reaction system impouring methyl alcohol, filtration drying, resulting PMMA presoma is dissolved again with trichloromethane, methanol extraction is to remove unreacted monomer, initiator and 1, the 1-diphenylethlene, the resulting polymers powder is placed 24h at vacuum drying oven.It is 21% that weighting method records monomeric transformation efficiency, products therefrom molecular weight and molecular weight distribution: Mn=11700, PDI=1.36;
2) in containing single tap reaction flask of magnetic agitation rotor, add the 0.5gPMMA presoma; 0.5g vinylformic acid and 20mL1; the 4-dioxane; mix the polymerization of under nitrogen protection, carrying out Acrylic Acid Monomer; 80 ℃ of temperature of reaction; reaction beginning post polymerization system becomes oyster white, along with the polymerization system oyster white of carrying out of reaction is deepened.In 6 hours reaction times, monomer conversion is 76%;
3) polymerization reaction system is cooled off, the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in a large amount of ethyl acetate, obtain PMMA presoma 0.11g, the mixture of separating obtained PMMA-b-PAA block polymer and PAA homopolymer is dispersed among the THF, separation does not obtain the explanation of PAA homopolymer does not have the PAA homopolymer to produce, and obtains PMMA-b-PAA Amphipathilic block polymer 0.77g.
1) with methyl methacrylate (0.2 mole), the catalyzer Diisopropyl azodicarboxylate 196.8mg (1.2 mmole) and 1 of 20.0g, 1-diphenylethlene 432mg (2.4 mmole) joins in the single tap reaction flask that contains the magnetic agitation rotor, under 80 ℃ of conditions, react 3h, stopped reaction also will precipitate in the reaction system impouring methyl alcohol, filtration drying, resulting PMMA presoma is dissolved again with trichloromethane, methanol extraction is to remove unreacted monomer, initiator and 1, the 1-diphenylethlene, the resulting polymers powder is placed 24h at vacuum drying oven.It is 19% that weighting method records monomeric transformation efficiency, products therefrom molecular weight and molecular weight distribution: Mn=10400, PDI=1.34;
2) in containing single tap reaction flask of magnetic agitation rotor, add 0.5g PMMA presoma, 2.5g vinylformic acid and 20mL1, the 4-dioxane, mix the polymerization of under nitrogen protection, carrying out Acrylic Acid Monomer, 80 ℃ of temperature of reaction, reaction beginning post polymerization system becomes oyster white, along with the polymerization system oyster white of carrying out of reaction is deepened, in 3 hours reaction times, monomer conversion is 21%;
3) polymerization reaction system is cooled off, the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in a large amount of ethyl acetate, obtain PMMA presoma 0.145g, the mixture of separating obtained PMMA-b-PAA block polymer and PAA homopolymer is dispersed among the THF, separation does not obtain the explanation of PAA homopolymer does not have the PAA homopolymer to produce, and obtains PMMA-b-PAA Amphipathilic block polymer 0.88g;
1) with methyl methacrylate (0.2 mole), the catalyzer Diisopropyl azodicarboxylate 196.8mg (1.2 mmole) and 1 of 20.0g, 1-diphenylethlene 432mg (2.4 mmole) joins in the single tap reaction flask that contains the magnetic agitation rotor, under 80 ℃ of conditions, react 3h, stopped reaction also will precipitate in the reaction system impouring methyl alcohol, filtration drying, resulting PMMA presoma is dissolved again with trichloromethane, methanol extraction is to remove unreacted monomer, initiator and 1, the 1-diphenylethlene, the resulting polymers powder is placed 24h at vacuum drying oven.It is 19% that weighting method records monomeric transformation efficiency, products therefrom molecular weight and molecular weight distribution: Mn=10400, PDI=1.34;
2) in containing single tap reaction flask of magnetic agitation rotor, add 0.5g PMMA presoma, 2.5g vinylformic acid and 20mL1, the 4-dioxane, mix the polymerization of under nitrogen protection, carrying out Acrylic Acid Monomer, 80 ℃ of temperature of reaction, reaction beginning post polymerization system becomes oyster white, along with the polymerization system oyster white of carrying out of reaction is deepened, in 6 hours reaction times, monomer conversion is 33%;
3) polymerization reaction system is cooled off, the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in a large amount of ethyl acetate, obtain PMMA presoma 0.095g, the mixture of separating obtained PMMA-b-PAA block polymer and PAA homopolymer is dispersed among the THF, separation does not obtain the explanation of PAA homopolymer does not have the PAA homopolymer to produce, and obtains PMMA-b-PAA Amphipathilic block polymer 1.23g.
1) with methyl methacrylate (0.2 mole), the catalyzer Diisopropyl azodicarboxylate 196.8mg (1.2 mmole) and 1 of 20.0g, 1-diphenylethlene 432mg (2.4 mmole) joins in the single tap reaction flask that contains the magnetic agitation rotor, under 80 ℃ of conditions, react 3h, stopped reaction also will precipitate in the reaction system impouring methyl alcohol, filtration drying, resulting PMMA presoma is dissolved again with trichloromethane, methanol extraction is to remove unreacted monomer, initiator and 1, the 1-diphenylethlene, the resulting polymers powder is placed 24h at vacuum drying oven.It is 19% that weighting method records monomeric transformation efficiency, products therefrom molecular weight and molecular weight distribution: Mn=10400, PDI=1.34;
2) in containing single tap reaction flask of magnetic agitation rotor, add 0.5g PMMA presoma, 2.5g vinylformic acid and 20mL1, the 4-dioxane, mix the polymerization of under nitrogen protection, carrying out Acrylic Acid Monomer, 70 ℃ of temperature of reaction, reaction beginning post polymerization system becomes oyster white, along with the polymerization system oyster white of carrying out of reaction is deepened; In 12 hours reaction times, monomer conversion is 39%;
3) polymerization reaction system is cooled off, the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in a large amount of ethyl acetate, obtain PMMA presoma 0.035g, the mixture of separating obtained PMMA-b-PAA block polymer and PAA homopolymer is dispersed among the THF, separate obtaining PAA homopolymer 0.16g, obtain PMMA-b-PAA Amphipathilic block polymer 1.32g.
1) with methyl methacrylate (0.2 mole), the catalyzer Diisopropyl azodicarboxylate 196.8mg (1.2 mmole) and 1 of 20.0g, 1-diphenylethlene 432mg (2.4 mmole) joins in the single tap reaction flask that contains the magnetic agitation rotor, under 80 ℃ of conditions, react 3h, stopped reaction also will precipitate in the reaction system impouring methyl alcohol, filtration drying, resulting PMMA presoma is dissolved again with trichloromethane, methanol extraction is to remove unreacted monomer, initiator and 1, the 1-diphenylethlene, the resulting polymers powder is placed 24h at vacuum drying oven.It is 19% that weighting method records monomeric transformation efficiency, products therefrom molecular weight and molecular weight distribution: Mn=10400, PDI=1.34;
2) in containing single tap reaction flask of magnetic agitation rotor, add 0.5g PMMA presoma, 2.5g vinylformic acid and 20mL1, the 4-dioxane, mix the polymerization of under nitrogen protection, carrying out Acrylic Acid Monomer, 80 ℃ of temperature of reaction, reaction beginning post polymerization system becomes oyster white, along with the polymerization system oyster white of carrying out of reaction is deepened, in 12 hours reaction times, monomer conversion is 85%;
3) polymerization reaction system is cooled off, the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in ethyl acetate, do not obtain the PMMA presoma, illustrate that the PMMA presoma is exhausted, the mixture of separating obtained PMMA-b-PAA block polymer and PAA homopolymer is dispersed among the THF, obtains PAA homopolymer 0.75g, PMMA-b-PAA Amphipathilic block polymer 1.87g.
Embodiment 8
1) with methyl methacrylate (0.2 mole), the catalyzer Diisopropyl azodicarboxylate 196.8mg (1.2 mmole) and 1 of 20.0g, 1-diphenylethlene 432mg (2.4 mmole) joins in the single tap reaction flask that contains the magnetic agitation rotor, under 90 ℃ of conditions, react 3h, stopped reaction also will precipitate in the reaction system impouring methyl alcohol, filtration drying, resulting PMMA presoma is dissolved again with trichloromethane, methanol extraction is to remove unreacted monomer, initiator and 1, the 1-diphenylethlene, the resulting polymers powder is placed 24h at vacuum drying oven.It is 25% that weighting method records monomeric transformation efficiency, products therefrom molecular weight and molecular weight distribution: Mn=9750, PDI=1.40;
2) in containing single tap reaction flask of magnetic agitation rotor, add 0.5g PMMA presoma, 0.5g vinylformic acid and 20mL1, the 4-dioxane, mix the polymerization of under nitrogen protection, carrying out Acrylic Acid Monomer, 80 ℃ of temperature of reaction, reaction beginning post polymerization system becomes oyster white, along with the polymerization system oyster white of carrying out of reaction is deepened, in 6 hours reaction times, monomer conversion is 82%;
3) polymerization reaction system is cooled off, the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in a large amount of ethyl acetate, obtain PMMA presoma 0.10g, the mixture of separating obtained PMMA-b-PAA block polymer and PAA homopolymer is dispersed among the THF, separation does not obtain the explanation of PAA homopolymer does not have the PAA homopolymer to produce, and obtains PMMA-b-PAA Amphipathilic block polymer 0.81g.
Embodiment 9
1) at first, methyl methacrylate (0.2 mole), catalyzer Diisopropyl azodicarboxylate 196.8mg (1.2 mmole) and 1 with 20.0g, 1-diphenylethlene 432mg (2.4 mmole) joins in the single tap reaction flask that contains the magnetic agitation rotor, under 90 ℃ of conditions, react 3h, stopped reaction also will precipitate in the reaction system impouring methyl alcohol, filtration drying, resulting PMMA presoma is dissolved again with trichloromethane, methanol extraction is to remove unreacted monomer, initiator and 1, the 1-diphenylethlene, the resulting polymers powder is placed 24h at vacuum drying oven.It is 25% that weighting method records monomeric transformation efficiency, products therefrom molecular weight and molecular weight distribution: Mn=9750, PDI=1.40;
2) in containing single tap reaction flask of magnetic agitation rotor, add 0.5g PMMA presoma, 2.5g vinylformic acid and 20mL1, the 4-dioxane, mix the polymerization of under nitrogen protection, carrying out Acrylic Acid Monomer, 70 ℃ of temperature of reaction, reaction beginning post polymerization system becomes oyster white, along with the polymerization system oyster white of carrying out of reaction is deepened, in 6 hours reaction times, monomer conversion is 25%;
3) polymerization reaction system is cooled off, the disappearance of system oyster white becomes colorless transparent, polymerization system is precipitated in a large amount of ethyl acetate, obtain PMMA presoma 0.16g, the mixture of separating obtained PMMA-b-PAA block polymer and PAA homopolymer is dispersed among the THF, separation does not obtain the explanation of PAA homopolymer does not have the PAA homopolymer to produce, and obtains PMMA-b-PAA Amphipathilic block polymer 0.97g.
Claims (5)
1, there is the method for preparing methyl methacrylate-vinylformic acid block polymer down in a kind of 1, it is characterized in that, may further comprise the steps:
1) preparation contains semiquinone formula structure polymethylmethacrylate presoma: with monomers methyl methacrylate MMA, initiator Diisopropyl azodicarboxylate AIBN and 1,1-diphenylethlene DPE adds in the reaction vessel, in 70～90 ℃, at normal pressure, under the nitrogen protection atmosphere, carry out the MMA Raolical polymerizable, wherein, MMA and AIBN amount of substance are than being 100:0.8～0.4, the ratio of AIBN and DPE amount of substance is 1:1.5～2, react after 3 hours polymerization system methanol extraction, filtration drying, resulting polymers dissolves with trichloromethane, behind methanol extraction, place vacuum drying oven 24h again, obtain the polymetylmethacrylate presoma;
2) preparation methyl methacrylate-vinylformic acid block polymer PMMA-b-PAA: the PMMA presoma that obtains in monomer vinylformic acid AA and the step 1) is dissolved in 1, in the 4-dioxane solvent, in 70～80 ℃, under normal pressure, nitrogen protection atmosphere, carry out the block polymerization reaction of monomer A A, reaction times is 3～12 hours, wherein, the mass ratio of monomer A A and PMMA presoma is 5～1:1;
3) after the polymerization reaction system cooling separation PMMA-b-PAA: with step 2), polymerization system is precipitated in ethyl acetate, remove residue PMMA presoma after, polymerization system is dispersed in the tetrahydrofuran THF, remove polyacrylic acid PAA homopolymer precipitation, obtain the PMMA-b-PAA block polymer.
2, method according to claim 1 is characterized in that, the MMA Raolical polymerizable temperature described in the step 1) is 80 ℃.
3, method according to claim 1 is characterized in that, MMA and AIBN amount of substance are than being 100:0.6 in the MMA Raolical polymerizable described in the step 1).
4, method according to claim 1 is characterized in that, AIBN and DPE amount of substance are than being 1:2 in the MMA Raolical polymerizable described in the step 1).
5, method according to claim 1 is characterized in that step 2) described in the block polymerization reaction of monomer A A in the mass ratio of monomer A A and PMMA presoma be 5:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432717A (en) * | 2011-09-23 | 2012-05-02 | 北京化工大学 | Carbon-carbon bond free radical macromolecule initiator and preparation method thereof |
| CN103319668A (en) * | 2013-06-25 | 2013-09-25 | 常州大学 | Preparation method of butyl methacrylate-dimethylaminoethyl methacrylate block copolymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432717A (en) * | 2011-09-23 | 2012-05-02 | 北京化工大学 | Carbon-carbon bond free radical macromolecule initiator and preparation method thereof |
| CN103319668A (en) * | 2013-06-25 | 2013-09-25 | 常州大学 | Preparation method of butyl methacrylate-dimethylaminoethyl methacrylate block copolymer |
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