CN102321198B - Method for preparing bimodal distribution polymer - Google Patents
Method for preparing bimodal distribution polymer Download PDFInfo
- Publication number
- CN102321198B CN102321198B CN 201110177187 CN201110177187A CN102321198B CN 102321198 B CN102321198 B CN 102321198B CN 201110177187 CN201110177187 CN 201110177187 CN 201110177187 A CN201110177187 A CN 201110177187A CN 102321198 B CN102321198 B CN 102321198B
- Authority
- CN
- China
- Prior art keywords
- raft
- bimodal distribution
- raft reagent
- molecular weight
- reagent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 CC=*C=C(CC(N[C+]=S)=C)C(C=*CC*)=C* Chemical compound CC=*C=C(CC(N[C+]=S)=C)C(C=*CC*)=C* 0.000 description 1
Images
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
The method discloses a method for preparing a bimodal distribution polymer. The method comprises the following steps of preparing a polymerization system, performing an RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization reaction at 50-90 DEG C for at least one hour, separating and purifying, and obtaining the bimodal distribution polymer, wherein the polymerization system comprises a monomer, a free radical initiating agent, a single head RAFT reagent and a double head RAFT reagent; the free radical initiating agent is one selected from styrene, acrylic, water soluble N-isopropyl acrylamide and the like; the conventional free radical initiating agent is one selected from azobisisobutyronitrile and benzoyl peroxide; and the single and double functional-group RAFT reagent combination is one selected from dithiocarbamate and trithiocarbonates. According to the invention, the bimodal distribution polymer with molecular weights and controllable molecular weight distribution can be synthesized because the used RAFT method has 'active'/controllable polymerization characteristics.
Description
Technical field
The present invention relates to the reversible addition of a kind of employing-fracture chain and shift the method for the synthetic bimodal distribution polymer of (Reversible Addition-Fragmentation Chain Transfer, RAFT) polymerization process.
Background technology
The molecular weight of polymkeric substance and molecular weight distributing index have determined its physicals, mechanical property and processing characteristics.The polymkeric substance of molecular weight has preferably toughness and flowing property, but the rigidity of polymkeric substance can decrease.The polymkeric substance that molecular weight is larger has preferably mechanical property, but its toughness can corresponding reduction.Even high molecular weight material demonstrates good toughness, but because their high melt viscosity, so that process very difficult.For some special application, usually need polymkeric substance to have simultaneously preferably mechanical property and processing characteristics.The shortcoming that can not have both in order to overcome use properties and processing characteristics, polymkeric substance by synthetic bimodal distribution, high molecular and low-molecular-weight polymkeric substance are namely arranged simultaneously, can be under many extreme conditions balance and optimize Drawing abillity (low molecular weight part) and use properties (high molecular part).Under processing temperature, low molecular weight part can improve the flowability of polymer materials in the polymkeric substance; Under use temperature, the high molecular part can improve the use properties of material in the polymkeric substance.The preparation method of bimodal distribution polymer generally includes following several:
(1) physical blending, this method are after synthesizing the polymkeric substance of high and low relative molecular mass respectively, again both are mixed (referring to: Xue Feng, Ma Guangsheng. broad peak or two sections polymerization polyvinyl resins of bimodal distribution performance study.
The modern plastics processed and applied,
2007, 19,13-16.)
(2) two-step reaction, its method refer under a kind of polymerizing condition first synthetic wherein a kind of polymkeric substance of relative molecular mass, then in the second step reaction, change the polymkeric substance that reaction conditions obtains another kind of relative molecular mass (referring to:
Abedi,?S.;?Hassanpour,?N.?Preparation?of?Bimodal?Polypropylene?in?Two-Step?Polymerization.?
J.?Appl.?Polym.?Sci.,
2006 ,?101,?1456-1462.）。
(3) use chain-transfer agent or linking agent etc., this method is generally synthesized first low-molecular weight polymer, then synthesize higher molecular weight polymer (referring to Tobita, H. Bimodal Molecular Weight Distribution Formed in the Emulsion Polymerization of Ethylene. in reaction system, adding chain-transfer agent or linking agent
J. Polym. Sci., Part A:Polym. Chem., 2002, 40,3426-3433.).
(4) make spent mixed catalyst or mixed catalyst system, the compound catalyst system that nickel and zirconium, titanium form after promotor methylaluminoxane (MAO) activation, can make the single ethylene polymerization prepare the polyethylene of bimodal pattern long-chain branch.Equally, iron, cobalt, chromium cpd are after using a large amount of MAO activation or use ziegler natta catalyst, also can prepare the polyethylene of bimodal distribution (referring to (a) Li, L.; Wang, Q. Synthesis of Polyethylene with Bimodal Molecular Weight Distribution by Supported Iron-Based Catalyst.
J. Polym. Sci., Part A:Polym. Chem.,
2004, 42,5662-5669. (b) Yamamoto, K.; Ishihama, Y.; Sakata, K. Preparation of Bimodal HDPEs with Metallocene on Cr-Montmorillonite Support
. J. Polym. Sci. Part A:Polym. Chem.,
2010, 48,3722-3728.).
Although these methods can successfully be synthesized the polymkeric substance of bimodal distribution, the two-step reaction method complicated operation contains toxic metal in the mixed catalyst law system, and process for synthetic catalyst is complicated, expensive.The most important thing is that above several method is difficult to synthetic molecular weight and the simultaneously controlled bimodal polymers of molecular weight distribution.
Reversible Addition-Fragmentation Chain Transfer(RAFT, being that reversible addition-fracture chain is shifted) polymerization process is as one of " activity "/controllable free radical polymerization process of tool potentiality, and it is proposed in 1998 years first by people such as Rizzardo.The RAFT polymerization is exactly to add suitable RAFT reagent in the radical polymerization system of routine, and used monomer, initiator, solvent and temperature of reaction are all consistent with conventional radical polymerization.Therefore it is the same with common radical polymerization, has to operate and aftertreatment is simple, the diversified advantage of polymerization methods, is one of " activity "/controllable free radical polymerization process of tool industrial prospect.From present existing report, still do not use the bibliographical information of the synthetic bimodal distribution polymer of RAFT method.
Summary of the invention
Goal of the invention of the present invention provides a kind of method for preparing bimodal distribution polymer.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of method for preparing bimodal distribution polymer may further comprise the steps: the preparation polymerization system, carried out the RAFT polyreaction at least 1 hour under 50～90 ℃, separating-purifying obtains bimodal distribution polymer;
Described polymerization system comprises monomer, radical initiator, single head RAFT reagent, double end RAFT reagent, wherein, n (monomer) ﹕ n (initiator) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=200 ~ 100000 ﹕ 1～30 ﹕ 1～150 ﹕ 1～150;
Wherein, described monomer is the monomer of free redical polymerization, is selected from: vinylbenzene, esters of acrylic acid, water miscible
NA kind of in the-N-isopropylacrylamide etc.; Described esters of acrylic acid is preferably: methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate or butyl methacrylate;
Described initiator is the conventional free radical initiator, is selected from: a kind of in Diisopropyl azodicarboxylate (AIBN), the dibenzoyl peroxide (BPO);
Described single head RAFT reagent is selected from: dithiocarbamate
Or trithiocarbonate class
In a kind of;
Described double end RAFT reagent is selected from: dithiocarbamate
Or trithiocarbonate class
In a kind of;
Wherein R, R
1, R
2Be selected from separately :-Ph ,-Ph-OCH
3,-(CH
3)
2A kind of in alkyl, naphthylene group or the carbazole group of C-C ≡ N, C1～C4; R
3Be selected from
,
,
Or
In a kind of, n=7～23 wherein.
In the technique scheme, can be by adjusting the molecular weight of reaction times control polymkeric substance.
In the technique scheme, can control by the molar ratio of adjusting single, double RAFT reagent the massfraction of high and low polydispersity polymer in the polymkeric substance.For example need to obtain the high-molecular weight polymer of more ratios, can realize by the ratio that increases double end RAFT reagent, on the contrary then opposite.
In the technique scheme, the narrow molecular weight distribution of resulting polymers (PDI＜1.2), the actual molecular weight of resulting polymers conforms to theoretical molecular.
In the technique scheme, described RAFT polyreaction can be carried out polymerization with body or solution polymerization mode.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention proposes to use the synthetic bimodal distribution polymer of method of " activity "/controllable free-radical polymerisation first, and the molecular weight of two kinds of polymkeric substance and molecular weight distribution are simultaneously controlled, and the bimodal distribution macromolecular material that mixes for molecular level provides a kind of novel method.
2. because the present invention has adopted the RAFT polymerization process, have the polymerization single polymerization monomer face width, polymerization methods is various and simple to operate, do not need complicated last handling process, stable in the air and this reaction of the used chemical reagent of the present invention can operate under air atmosphere, is convenient to suitability for industrialized production.
3. because in the polymerization system of the present invention, the ratio of single, double RAFT reagent is adjustable, can synthesize the adjustable bimodal polymers of massfraction of high and low molecular weight.
4. because the present invention has adopted the RAFT polymerization system, and the molecular weight of resulting polymers can design easily, and polymer terminal group still has activity, can be used to the more synthetic activity/controlled block with topological framework, graft copolymer.
Description of drawings
Fig. 1 is reaction kinetics figure (1a) and transformation efficiency and the molecular weight graph of a relation (1b) of the synthetic bimodal distribution polymer of single, double RAFT agent combination of dithiocarbamate among the embodiment one;
Fig. 2 is the nuclear-magnetism figure of bimodal distribution polymer among the embodiment four;
Fig. 3 is reaction kinetics figure (3a) and transformation efficiency and the molecular weight graph of a relation (3b) of the synthetic bimodal distribution polymer of single, double RAFT agent combination of trithiocarbonate class among the embodiment five.
Embodiment
The invention will be further described below in conjunction with drawings and Examples:
Used chemical reagent among the embodiment: vinylbenzene (St), 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Carbazole, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Diisopropyl azodicarboxylate (AIBN), 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Resorcinol, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Dithiocarbonic anhydride, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Methyl-sulphoxide, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Tetrahydrofuran (THF) (THF), methylene dichloride and methyl alcohol, analytical pure, Changshu City Yang Yuan chemical reagent company limited; Triethylamine, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Benzyl sulfhydrate, propylmercaptan, 99%, China Medicine (Group) Shanghai Chemical Reagent Co.; Isosorbide-5-Nitrae-chloromethylbenzene, cylite, 99%, China Medicine (Group) Shanghai Chemical Reagent Co..
Testing tool and condition:
Gel permeation chromatograph: the 1515 type GPC of U.S. Waters (Waters); Condition determination: HR1, HR3 and the series connection of HR4 three posts are used, the differential detector, moving phase is tetrahydrofuran (THF) (1mL/min), 30 ℃ of column temperatures are done correction with polymethylmethacrylate or polystyrene standards.
Nuclear magnetic resonance analyser: 400 megahertzes; Condition determination: with CDCl
3Be solvent, take tetramethylsilane as internal standard substance, probe temperature is room temperature.
Embodiment one: with the synthetic bimodal distribution polystyrene (PS) of the dithiocarbamate of the equimolar ratio example RAFT of single, double functional group agent combination
By proportioning n (St) ﹕ n (AIBN) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=200～2000 ﹕ 1 ﹕ 1 ~ 20 ﹕ 1 ~ 10, add successively single head RAFT reagent, double end RAFT reagent, AIBN, St is in the ampoule of 5 mL, after passing into 15 minutes nitrogen, tube sealing under anaerobic atmosphere (mass polymerization).Place the oil bath under the steady temperature (75 ℃) to react by predetermined time the ampoule behind the tube sealing.After reacting end, take out tube sealing, with the cold water cooling, open tube sealing immediately, with the tetrahydrofuran (THF) dissolving of 2 ~ 5 mL, pour in the methyl alcohol of 250 mL, the rear suction filtration of the placement of spending the night, washing, oven dry can obtain the polystyrene of " activity ";
Wherein, representational single head RAFT agent structure is in the dithiocarbamate
Representational bifunctional RAFT agent structure is in the dithiocarbamate:
Fig. 1 is the reaction kinetics figure of the synthetic bimodal distribution polymer of RAFT method; Polymerizing condition is: St=3mL, [St]
0/ [AIBN]
0/ [single head RAFT reagent]
0/ [double end RAFT reagent]
0=1200:1:2.5:2.5, T=75 ℃, anaerobic.By Fig. 2 a and Fig. 2 b as can be known: the concentration of the free radical of deriving in the reaction process keeps constant, and high and low polydispersity polymer conforms to corresponding theoretical molecular, and molecular weight distribution is narrower.High and low polydispersity polymer is the linear growth along with the growth of polymerization time all, and polymerization process can be controlled the molecular weight of polymkeric substance preferably.Simultaneously also can find out no matter be the polymkeric substance that under high and low monomer conversion condition, all can obtain bimodal distribution.
Embodiment two: single, double RAFT agent combination of the dithiocarbamate under the different mol ratio example (the RAFT reagent type is with embodiment one) synthesized bimodal distribution polystyrene (PS)
By proportioning n (St) ﹕ n (AIBN) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=200 ~ 10000 ﹕ 1 ~ 30 ﹕ 1 ~ 150 ﹕ 150 ~ 1, add successively single head RAFT reagent, double end RAFT reagent, AIBN, St is in the ampoule of 5 mL, after passing into 15 minutes nitrogen, tube sealing under anaerobic atmosphere (mass polymerization).Place the oil bath under the steady temperature (75 ℃) to react by predetermined time the ampoule behind the tube sealing.After reacting end, take out tube sealing, with the cold water cooling, open tube sealing immediately, with the tetrahydrofuran (THF) dissolving of 2 ~ 5 mL, pour in the methyl alcohol of 250 mL, the rear suction filtration of the placement of spending the night, washing, oven dry can obtain the polystyrene of " activity ".
The data of embodiment two see Table 1.
The result of the synthetic bimodal distribution polystyrene of single, double RAFT agent combination of table 1. different mol ratio example
Reaction conditions: 3.0 mL vinylbenzene, mass polymerization, 75 ℃ of temperature of reaction.
A)R=[St]
0/ [AIBN]
0/ [single head RAFT reagent]
0/ [double end RAFT reagent]
0
B)Low-molecular weight polymer/high-molecular weight polymer;
M N, thBe the molecular weight that Theoretical Calculation draws, the molecular weight of low-molecular weight polymer=([St]
0/ [RAFT group]
0) *
M W, St* transformation efficiency %+
M W, single head RAFT reagent, high-molecular weight polymer molecular weight=2 * ([St]
0/ [RAFT group]
0) *
M W, St* transformation efficiency %+
M W, double end RAFT reagent M N, GPCTest the molecular weight that draws for gel permeation chromatography (GPC);
C)Low-molecular weight polymer/high-molecular weight polymer;
M w/
M nTest the molecular weight distributing index that draws for gel permeation chromatography (GPC).
Can be found out that by data in the table 1 when adding the single, double RAFT of the functional group reagent of different mol ratio example in system, reaction still is controlled.Such as single head RAFT reagent: during double end RAFT reagent=1:100, still can obtain bimodal distribution polymer, reaction system PDI is still very low.
Embodiment three: the bimodal distribution polystyrene of single, double RAFT agent combination of dithiocarbamate (the RAFT reagent type is with embodiment one) synthetic macromolecule amount.
By proportioning n (St) ﹕ n (AIBN) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=10000 ~ 100000 ﹕ 1 ﹕ 2～10 ﹕ 2～10, add successively single head RAFT reagent, double end RAFT reagent, AIBN, St is in the ampoule of 5 mL, after passing into 15 minutes nitrogen, tube sealing under anaerobic atmosphere (mass polymerization).Place the oil bath under the steady temperature (75 ℃) to react by predetermined time the ampoule behind the tube sealing.After reacting end, take out tube sealing, with the cold water cooling, open tube sealing immediately, with the tetrahydrofuran (THF) dissolving of 2 ~ 5 mL, pour in the methyl alcohol of 250 mL, the rear suction filtration of the placement of spending the night, washing, oven dry can obtain the polystyrene of " activity ".
The data of embodiment three see Table 2.
The polymerization result of table 2. synthetic macromolecule amount bimodal polystyrene
Reaction conditions: 12.0 mL vinylbenzene, mass polymerization, 75 ℃ of temperature of reaction.
A)R=[St]
0/ [AIBN]
0/ [single head RAFT reagent]
0/ [double end RAFT reagent]
0
B)Low-molecular weight polymer/high-molecular weight polymer;
M N, thBe the molecular weight that Theoretical Calculation draws, the molecular weight of low-molecular weight polymer=([St]
0/ [RAFT group]
0) *
M W, St* transformation efficiency %+
M W, single head RAFT reagent, high-molecular weight polymer molecular weight=2 * ([St]
0/ [RAFT group]
0) *
M W, St* transformation efficiency %+
M W, double end RAFT reagent M N, GPCTest the molecular weight that draws for gel permeation chromatography (GPC);
C)Low-molecular weight polymer/high-molecular weight polymer;
M W/ M nTest the molecular weight distributing index that draws for gel permeation chromatography (GPC).
Can be found out that by data in the table 2 when using the bimodal polymers of RAFT method synthetic macromolecule amount, when molecular weight was higher, reaction still was controlled, reaction system PDI is still very low.
Embodiment four: the nuclear magnetic spectrogram of the synthetic bimodal distribution polystyrene of single, double RAFT agent combination of dithiocarbamate (the RAFT reagent type is with embodiment one).
In living polymerization, the nuclear magnetic spectrogram of polymkeric substance is used for the end group of polymkeric substance is analyzed, with the living polymerization feature of checking polymkeric substance.
Carry out the nuclear-magnetism test of polystyrene according to well known to a person skilled in the art experimental procedure.Test result such as Fig. 2 show that the end of bimodal distribution polymer is with RAFT reagent group.
Embodiment five: with the synthetic bimodal distribution polystyrene (PS) of the trithiocarbonate class RAFT of the single, double functional group agent combination of equimolar ratio example
By proportioning n (St) ﹕ n (AIBN) ﹕ n (single head RAFT reagent) ﹕ n (double end RAFT reagent)=200～2000 ﹕ 1 ﹕ 1 ~ 20 ﹕ 1 ~ 10, add successively single head RAFT reagent, double end RAFT reagent, AIBN, St is in the ampoule of 5 mL, after passing into 15 minutes nitrogen, tube sealing under anaerobic atmosphere (mass polymerization).Place the oil bath under the steady temperature (75 ℃) to react by predetermined time the ampoule behind the tube sealing.After reacting end, take out tube sealing, with the cold water cooling, open tube sealing immediately, with the tetrahydrofuran (THF) dissolving of 2 ~ 5 mL, pour in the methyl alcohol of 250 mL, the rear suction filtration of the placement of spending the night, washing, oven dry can obtain the polystyrene of " activity ";
Wherein, representational simple function group RAFT agent structure is in the trithiocarbonate class:
Representational bifunctional RAFT agent structure is in the trithiocarbonate class:
Fig. 3 is the ln ([M] of 75 ℃ of lower RAFT method polymerization St
0/ [M])-dynamic curve.Be illustrated as the first order kinetics of monomer concentration, show that the number of free radical of deriving is constant in polymerization process.Simultaneously, also can be observed inductive phase (≈ 7.5 h) among Fig. 3 a.According to RAFT polymerization-filling mechanism, reaction AIBN in early stage decomposes the free radical that produces may be combined with trithiocarbonate RAFT reagent, and the intermediate rate of decomposition of formation is slower, thereby the inductive phase of a very long time occurs.But along with the carrying out of reaction, derive in the system free radical and RAFT reagent are finally set up a reversible running balance.The molecular weight that can also significantly find out polymkeric substance from Fig. 3 b increases along with monomer conversion is linear, and the PS of preparation still have narrower molecular weight distributing index (
M w/
M n) (＜1.4).Molecular weight obtains theoretical molecular with mol ratio calculating according to the initial concentration of St and RAFT reagent and is close.More than these all show and use single, double trithiocarbonate class RAFT reagent can synthesize bimodal distribution polymer.
Claims (3)
1. a method for preparing bimodal distribution polymer is characterized in that, may further comprise the steps: the preparation polymerization system, under 50～90 ℃, carried out the RAFT polyreaction at least 1 hour, and separating-purifying obtains bimodal distribution polymer;
Described polymerization system comprises monomer, radical initiator, single head RAFT reagent, double end RAFT reagent, wherein, with molar ratio computing, Dan Ti ﹕ Yin Fa Ji ﹕ single head RAFT Shi Ji ﹕ double end RAFT reagent=200～100000 ﹕, 1～30 ﹕, 1～150 ﹕ 1～150;
Wherein, described monomer is the monomer of free redical polymerization, and described initiator is the conventional free radical initiator;
Described single head RAFT reagent is
,
Described double end RAFT reagent is
Perhaps, described single head RAFT reagent is
,
Described double end RAFT reagent is
2. the described method for preparing bimodal distribution polymer according to claim 1 is characterized in that described monomer is selected from: vinylbenzene, esters of acrylic acid, water miscible
NA kind of in the-N-isopropylacrylamide.
3. the described method for preparing bimodal distribution polymer according to claim 1 is characterized in that described initiator is the conventional free radical initiator, is selected from: a kind of in Diisopropyl azodicarboxylate, the dibenzoyl peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110177187 CN102321198B (en) | 2011-06-28 | 2011-06-28 | Method for preparing bimodal distribution polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110177187 CN102321198B (en) | 2011-06-28 | 2011-06-28 | Method for preparing bimodal distribution polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102321198A CN102321198A (en) | 2012-01-18 |
| CN102321198B true CN102321198B (en) | 2013-05-29 |
Family
ID=45449053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110177187 Expired - Fee Related CN102321198B (en) | 2011-06-28 | 2011-06-28 | Method for preparing bimodal distribution polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102321198B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6410803B2 (en) * | 2013-09-20 | 2018-10-24 | スリーエム イノベイティブ プロパティズ カンパニー | Trithiocarbonate-containing addition-cleavage agent |
| CN110606902B (en) * | 2019-07-29 | 2021-08-24 | 长兴电子（苏州）有限公司 | Novel macromolecular photoinitiator and synthesis method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020729A (en) * | 2007-03-26 | 2007-08-22 | 浙江大学 | Process of preparing polybutyl acrylate with narrow molecular weight distribution |
| CN102083863B (en) * | 2008-03-07 | 2014-10-22 | 卡内基梅隆大学 | Improved controlled radical polymerization processes |
-
2011
- 2011-06-28 CN CN 201110177187 patent/CN102321198B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102321198A (en) | 2012-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | RAFT-mediated one-pot aqueous emulsion polymerization of methyl methacrylate in presence of poly (methacrylic acid-co-poly (ethylene oxide) methacrylate) trithiocarbonate macromolecular chain transfer agent | |
| Aksakal et al. | Pentablock star shaped polymers in less than 90 minutes via aqueous SET-LRP | |
| Ferreira et al. | Optimizing the generation of narrow polydispersity ‘arm-first’star polymers made using RAFT polymerization | |
| Öztürk et al. | One‐step synthesis of block‐graft copolymers via simultaneous reversible‐addition fragmentation chain transfer and ring‐opening polymerization using a novel macroinitiator | |
| KR20010090759A (en) | Multimodal polymers by controlled radical polymerization in the presence of alkoxyamines | |
| CN101528782A (en) | Acid functionalized gradient block copolymers | |
| Bray et al. | Anionic multiblock core cross-linked star copolymers via RAFT polymerization | |
| Zhang et al. | Hybrid copolymerization via mechanism interconversion between radical vinyl-addition and anion ring-opening polymerization | |
| Boyer et al. | Synthesis of complex macromolecules using iterative copper (0)‐mediated radical polymerization | |
| Zhou et al. | Facile synthesis of gradient copolymers via semi-batch copper (0)-mediated living radical copolymerization at ambient temperature | |
| CN110804143A (en) | Method for preparing block polymer nanoparticles based on controllable free radical polymerization | |
| Palmiero et al. | The RAFT copolymerization of acrylic acid and acrylamide | |
| Bertrand et al. | Cu (0)-mediated living radical polymerisation in dimethyl lactamide (DML); an unusual green solvent with limited environmental impact | |
| CN102321198B (en) | Method for preparing bimodal distribution polymer | |
| CN101891843B (en) | Preparation method of hyperbranched polyvinyl acetate | |
| Savelyeva et al. | Pyrrolidone‐functional smart polymers via nitroxide‐mediated polymerization | |
| JP2021524872A (en) | High melt index thermoplastic elastomer and its manufacturing method | |
| CN104031214A (en) | St/MAH-g-MMA (styrene/maleic anhydride-grafted-methyl methacrylate) graft copolymer, and preparation method and application thereof | |
| CN104628948A (en) | Acrylate-type poly-chain transfer agent as well as preparation method and application of poly-chain transfer agent in preparation of columnar polymer brush | |
| Mei et al. | Nitroxide‐Mediated Polymerization of 2‐Hydroxyethyl Methacrylate (HEMA) Controlled with Low Concentrations of Acrylonitrile and Styrene | |
| CN107163203B (en) | A kind of multiform looks organic nano particle and its preparation method and application | |
| CN111253536A (en) | Polypropylene triblock copolymer responding to temperature and pH and preparation method thereof | |
| CN102432745B (en) | Method for preparing active copolymer containing double functional groups including epoxy and tertiary amine | |
| CN102603948B (en) | Polyvinyl pyridine preparing method | |
| Feng et al. | Synthesis of 6‐Armed Amphiphilic Block Copolymers with Styrene and 2, 3‐Dihydroxypropyl Acrylate by Atom Transfer Radical Polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: Suzhou City, Jiangsu province 215137 Xiangcheng District Ji Road No. 8 Patentee after: Soochow University Address before: 215123 Suzhou City, Suzhou Province Industrial Park, No. love road, No. 199 Patentee before: Soochow University |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130529 Termination date: 20160628 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |