CN102432722B - Method for preparing rosin-based regular polymers - Google Patents
Method for preparing rosin-based regular polymers Download PDFInfo
- Publication number
- CN102432722B CN102432722B CN201110300950.2A CN201110300950A CN102432722B CN 102432722 B CN102432722 B CN 102432722B CN 201110300950 A CN201110300950 A CN 201110300950A CN 102432722 B CN102432722 B CN 102432722B
- Authority
- CN
- China
- Prior art keywords
- monomer
- rosin
- rosinyl
- polymers
- radical polymerization
- 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
Images
Abstract
The invention discloses a method for preparing rosin-based regular polymers. The method comprises the following steps of: dissolving a rosin-based monomer, an initiator for free radical polymerization, and a reversible addition-fragmentation chain transfer reagent in a certain molar mass ratio in a solvent, introducing nitrogen to remove oxygen, reacting at the temperature of between 50 and 120 DEG C for 1 to 24h, precipitating polymers in methanol, and filtering and drying to obtain rosin-based polymers with different molecular weights, wherein the rosin-based monomer is a rosin derivative which can be subjected to free radical polymerization reaction. By the method, the rosin-based regular polymers with different molecular weights and molecular weight distributions (PDI) can be obtained. The polymers are taken as prepolymers of a functional rosin block polymer.
Description
Technical field
The present invention relates to a kind of preparation method of rosin-based regular polymers, particularly a kind of new polymerization process is in the synthetic application of rosinyl polymkeric substance.
Background technology
Rosin is a kind of important renewable data, one of afforestation product that Ye Shi China is main, and world's rosin annual production is about 1,200,000 tons, approximately 800,000 tons of China's rosin annual production.Rosin is mainly by wanting resinous acid and part neutrals to form, and carboxyl and conjugated double bond are the main functional group in resinous acid.Chemical modification by carboxyl and conjugated double bond has been synthesized the deep processed products such as nilox resin, staybelite, maleated rosin, acrylic acid rosin and various rosin esters, wherein also comprise that some can carry out the monomer (CN101215445 of radical polymerization, CN101492591, CN101265392, CN101066918).As follows:
In conventional radical polymerization system, chain transfer reaction is irreversible, causes the polymerization degree to reduce, and molecular weight and molecular structure are uncontrollable.Reversible addition-fracture chain transfer polymerization (Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT)) is a kind of important method of activity/controllable free-radical polymerisation (CRP), and it has the advantages such as applicable monomer scope is wide.Except common monomer, vinylformic acid, to the protic monomers such as vinylbenzenesulfonic acid sodium, hydroxyethyl methylacrylate, methacrylic acid amido ethyl ester or acid, all polymerizations smoothly of alkaline monomer, but also not for the polymerization of rosin based material.
RAFT reacts mainly by monomer, contrary addition-fracture chain transfer agents (RAFT reagent) and initiator composition.
RAFT reagent has dithiobenzoic acid isopropyl phenyl ester (CDB), dithio benzyl benzoate (BDTB), dithio toluylic acid isopropyl phenyl ester (CPDA), dithiobenzoic acid-1-ethoxycarbonyl-n-propyl (EPDTB), dibenzyl trithiocarbonate (DBTTC), S, S '-bis-(α-methyl phenyl ketone) trithiocarbonate (DNTTC) etc.Initiator has Diisopropyl azodicarboxylate, benzoyl peroxide, Ammonium Persulfate 98.5, Potassium Persulphate etc.
Rosin based monomer and conventional esters of acrylic acid or vinyl monomer comparison, one the three luxuriant and rich with fragrance structure of ring on molecular structure, has certain sterically hinderedly, affects the structure control of rosin based monomer in controllable polymerization.Therefore in the selection to RAFT reagent, the control of temperature of reaction is difficult point and the gordian technique of the regular rosinyl polymkeric substance of preparation.
Summary of the invention
In order to prepare regular type rosin polymer, the invention discloses a kind of preparation method of rosin-based regular polymers, adopt RAFT polymerization methods to prepare regular type rosin polymer, be the deep processing and utilization based theoretical of rosin.
Technical scheme of the present invention is: a kind of preparation method of rosin-based regular polymers, by rosinyl monomer, radical polymerization share initiator, reversible addition-fracture chain transfer agents is dissolved in solvent in certain molar mass ratio, and logical nitrogen is removed oxygen, after 50～120 ℃ of reaction 1～24h, polymkeric substance is precipitated in methyl alcohol, then filter, be dried the rosinyl polymkeric substance that obtains different molecular weight, described rosinyl monomer is the rosin derivative that can carry out Raolical polymerizable.Can obtain the rosin-based regular polymers of different molecular weight and molecular weight distribution (PDI) by present method.
Described rosinyl monomer is the Abietyl modified compound that contains acrylate, methacrylic ester, vinyl, allyl group or methyl alkenyl-functional groups;
It is Diisopropyl azodicarboxylate, benzoyl peroxide, Ammonium Persulfate 98.5 that described radical polymerization share initiator, and the free crowd that Potassium Persulphate etc. are conventional draws the one in agent.
Described reversible addition-fracture chain transfer agents (RAFT reagent) is dithiobenzoic acid isopropyl phenyl ester (CDB), dithio benzyl benzoate (BDTB), dithio toluylic acid isopropyl phenyl ester (CPDA), dithiobenzoic acid-1-ethoxycarbonyl-n-propyl (EPDTB), dibenzyl trithiocarbonate (DBTTC), S, S '-bis-(α-methyl phenyl ketone) trithiocarbonate (DNTTC) etc.
Described rosinyl monomer, reversible addition-fracture chain transfer agents and radical polymerization share initiator according to mol ratio rosinyl monomer: RAFT: radical polymerization share initiator=(2000～20): 1: the ratio of (1～0.1) is used.
Described solvent is tetrahydrofuran (THF) or toluene.
Beneficial effect:
(1) molecular size range of rosinyl polymkeric substance is determined by transformation efficiency, and molecular weight is along with the transformation efficiency of rosinyl monomer presents linear growth;
(2) molecular weight of loose base based polyalcohol can regulate by ratio and the final monomer conversion of controlling monomer and RAFT reagent;
(3) loose base based polyalcohol can be used as macromole evocating agent, reacts synthetic rosin functional type block polymer by RAFT; Be the hydrophobic prepolymer that a class has ordered structure, take rosin prepolymer as Macro RAFT agent, again by RAFT mode, can carry out the structure design of amphiphilic cpds.
(4) for the monomer RAFT polymerization of DAME, using toluene as solvent, under low temperature (78～80 ℃), polymer architecture control ratio is better.
Accompanying drawing explanation
Fig. 1 is embodiment 1 rosinyl monomer DAME regular polymer
1h NMR figure.
Fig. 2 is the kinetic curve of rosinyl monomer DAME polymkeric substance in embodiment 1.
Fig. 3 is rosinyl monomer DAME polymer kinetics GPC curve in embodiment 1.
Fig. 4 is rosinyl monomer DAME polymkeric substance GPC curve in embodiment 2
Fig. 5 is the kinetic curve of rosinyl monomer DAME polymkeric substance in embodiment 2.
Fig. 6 is the kinetic curve of rosinyl monomer DAME polymkeric substance in embodiment 3.
Fig. 7 is embodiment 5 rosinyl monomer DAE regular polymers
1h NMR figure.
Fig. 8 is embodiment 6 rosinyl monomer DAB regular polymers
1h NMR figure.
Fig. 9 is embodiment 1 rosinyl monomer DAME regular polymer contact angle figure.
Figure 10 is embodiment 5 rosinyl monomer DAE regular polymer contact angle figure.
Embodiment
Illustrate it in order better to implement spy of the present invention, but be not limitation of the present invention.
The RAFT reagent using in the present invention is self-control, with reference to preparing with Publication about Document: (1) Xiuqiang Xin, Yanmei Wang, Wei Liu, Synthesis of zwitterionic block copolymers via RAFT polymerization.European Polymer Journal, Volume 41, Issue 7, July 2005, Pages 1539-1545, (2) Andr é J.P.van Zyl, Rutger F.P.Bosch, James B.McLeary, Ronald D.Sanderson, Bert Klumperman.Sythesis of styrene based liquid-filled polymeric nanocapsules by the use of RAFT-mediated polymerization in miniemulsion.Polymer, Volume 46, Issue 11, 11May 2005, Pages 3607-3615. (3) Adam E. Smith, Xuewei Xu, Charles L.McCormick.Stimuli-responsive amphiphilic (co) polymers via RAFT polymerization.Progress in Polymer Science, Volume 35, Issues 1-2, January-February 2010, Pages 45-93.
By DAME monomer 10g, RAFT reagent (CDB, dithiobenzoic acid isopropyl phenyl ester) 66mg and AIBN (Diisopropyl azodicarboxylate) 4.0mg, example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 70 ℃, react after 24 hours monomer conversion 95%.Polymericular weight: M
n(GPC): 25600g/mol, PDI=1.22.Mn (NMR): 37800g/mol.
By DAME monomer 10g, RAFT reagent (CDB, dithiobenzoic acid isopropyl phenyl ester) 66mg and AIBN (Diisopropyl azodicarboxylate) 4.0mg, example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 100 ℃, react after 12 hours monomer conversion 35%.Polymericular weight: M
n(GPC): 10,600g/mol, PDI=1.29.M
n(NMR): 12900g/mol.
React after 24 hours monomer conversion 45%.Polymericular weight: M
n(GPC): 15,300g/mol, PDI=1.67.M
n(NMR): 17900g/mol.
From reaction, can find out, using toluene as solvent, 100 ℃ of reactions, reaction is at low conversion rate in 35% time, and polymerization process is controlled, and when transformation efficiency continues to raise, PDI raises, and it is uncontrollable that structure becomes.
By DAME monomer 10g, RAFT reagent (CDB, dithiobenzoic acid isopropyl phenyl ester) 66mg and AIBN (Diisopropyl azodicarboxylate) 4.0mg, example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml tetrahydrofuran (THF) in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 80 ℃, react after 12 hours polymkeric substance is precipitated in methyl alcohol, then filter, be dried the rosinyl polymkeric substance that obtains different molecular weight, monomer conversion 42%.Polymericular weight: M
n(GPC): 8600g/mol, PDI=1.46.M
n(NMR): 17000g/mol
By DAME monomer 10g, RAFT reagent (CDB, dithiobenzoic acid isopropyl phenyl ester) 66mg and AIBN (Diisopropyl azodicarboxylate) 4.0mg, example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml tetrahydrofuran (THF) in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 80 ℃, react after 24 hours monomer conversion 80%.Polymericular weight: M
n(GPC): 23000g/mol, PDI=1.82.Mn (NMR): 31800g/mol.
By DAE monomer 10g, RAFT reagent (CDB, dithiobenzoic acid isopropyl phenyl ester) 68.3mg and AIBN (Diisopropyl azodicarboxylate) 4.1mg, example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 80 ℃, react after 23 hours monomer conversion 88%.Polymericular weight: M
n(GPC): 29,100g/mol, PDI=1.3.M
n(NMR): 35000g/mol.
By DAB monomer 10g, RAFT reagent (CDB, dithiobenzoic acid isopropyl phenyl ester) 63.8mg and AIBN (Diisopropyl azodicarboxylate) 3.85mg, example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 70 ℃, react after 24 hours monomer conversion 73%.Polymericular weight: M
n(GPC): 7100g/mol, PDI=1.46.M
n(NMR): 31000g/mol.
By DAA monomer 10g, RAFT reagent (CDB, dithiobenzoic acid isopropyl phenyl ester) 80.0mg and AIBN (Diisopropyl azodicarboxylate) 4.82mg, example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 70 ℃, react after 24 hours monomer conversion 51%.Polymericular weight: M
n(GPC): 6100g/mol, PDI=1.52.M
n(NMR): 17300g/mol.
By DAMA monomer 10g, RAFT reagent (CDB, dithiobenzoic acid isopropyl phenyl ester) 76.8mg and AIBN (Diisopropyl azodicarboxylate) 4.64mg, example ([DAME]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 70 ℃, react after 24 hours monomer conversion 57%.Polymericular weight: M
n(GPC): 6100g/mol, PDI=1.47.M
n(NMR): 20300g/mol.
Embodiment 9
By DAE monomer 10g, RAFT reagent (BDTB, dithio benzyl benzoate) 61.3mg and AIBN (Diisopropyl azodicarboxylate) 4.12mg, example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 70 ℃, react after 24 hours monomer conversion 86%.Polymericular weight: M
n(GPC): 19100g/mol, PDI=1.39.M
n(NMR): 34200g/mol.
Embodiment 10
By DAE monomer 10g, RAFT reagent (CPDA, dithio toluylic acid isopropyl phenyl ester) 71.8mg and AIBN (Diisopropyl azodicarboxylate) 4.12mg, example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 70 ℃, react after 24 hours monomer conversion 91%.Polymericular weight: M
n(GPC): 22600g/mol, PDI=1.47.M
n(NMR): 36200g/mol.
Embodiment 11
By DAE monomer 10g, RAFT reagent (EPDTB, dithiobenzoic acid-1-ethoxycarbonyl-n-propyl) 70.8mg and AIBN (Diisopropyl azodicarboxylate) 4.12mg, example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 70 ℃, react after 24 hours monomer conversion 87%.Polymericular weight: M
n(GPC): 18600g/mol, PDI=1.53.M
n(NMR): 34600g/mol.
By DAE monomer 10g, RAFT reagent (DBTTC, dibenzyl trithiocarbonate), 72.8mg and AIBN (Diisopropyl azodicarboxylate) 4.12mg, example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 70 ℃, react after 24 hours monomer conversion 83%.Polymericular weight: M
n(GPC): 16700g/mol, PDI=1.62.M
n(NMR): 33000g/mol.
By DAE monomer 10g, RAFT reagent (DBTTC, dibenzyl trithiocarbonate), 86.9mg and AIBN (Diisopropyl azodicarboxylate) 4.12mg, example ([DAE]: [CDB]: [AIBN]=[100]: [1]: [0.1]) adds in 20ml toluene in molar ratio, forward in eggplant type reaction flask nitrogen bubble deoxygenation 15 minutes to by molten.Then at 70 ℃, react after 24 hours monomer conversion 80%.Polymericular weight: M
n(GPC): 14700g/mol, PDI=1.58.M
n(NMR): 31800g/mol.
With the solvent of water, the rosinyl regularity matrix material of embodiment 1, embodiment 5 and embodiment 6 is carried out to contact angle test, experimental result shows, and all contact angle numerical value is all greater than 90 degree, and this shows that rosinyl regularity matrix material has good hydrophobicity.
Spectrum analysis
Fig. 1 is embodiment 1 rosinyl monomer DAME regular polymer
1h NMR figure is that 5.0ppm does not contain monomer in the proton peak that there is no vinyl between 6.5ppm illustrates polymkeric substance in chemical shift;
The kinetic curve of rosinyl monomer DAME polymkeric substance in Fig. 2 embodiment 1.Kinetic curve is linear, shows that this reaction is living polymerization;
Rosinyl monomer DAME polymer kinetics GPC curve in Fig. 3 embodiment 1, GPC curve shows the prolongation along with the reaction times, and the transformation efficiency of monomer increases, and molecular weight increases.
In Fig. 4 embodiment 2, rosinyl monomer DAME reacts 12 hours post polymerization thing GPC curves at 100 ℃, and molecular weight is M
n(GPC): 10,600g/mol, PDI=1.29;
Fig. 5 is the kinetic curve that in embodiment 2, rosinyl monomer DAME reacts at 100 ℃, and showing to only have this polyreaction in the time that reaction conversion ratio is below 35% from dynamics research is active reaction, and reaction process is controlled.When reaction conversion ratio is higher than 35% time, transformation efficiency is almost constant, that is to say that polyreaction stops.
Fig. 6 is the kinetic curve that in embodiment 3, rosinyl monomer DAME reacts at 80 ℃.Kinetic curve shows that polymerization rate improves, and simultaneous reactions starts slower, comparison diagram 2 and Fig. 6, and in Fig. 2, at 70 ℃, the kinetic curve linear relationship of reaction is better, and this shows that the polyreaction of MAEDA is more suitable for carrying out at relatively low temperature.
Fig. 7 is embodiment 5 rosinyl monomer DAME regular polymers
1h NMR figure is that 5.0ppm does not contain monomer in the proton peak that there is no vinyl between 6.5ppm illustrates polymkeric substance in chemical shift;
Fig. 8 is embodiment 6 rosinyl monomer DAB regular polymers
1h NMR figure is that 5.0ppm does not contain monomer in the proton peak that there is no vinyl between 6.5ppm illustrates polymkeric substance in chemical shift.
Contact angle numerical value in Fig. 8, Fig. 9 and Figure 10 is more than 90 degree, showed that rosinyl polymkeric substance prepared by RAFT polymerization was the hydrophobic prepolymer that a class has ordered structure, it can make Macro RAFT agent, and another segment polymer of grafting, realizes the design of molecular structure.
Claims (3)
1. the preparation method of a rosin-based regular polymers, it is characterized in that, by rosinyl monomer, radical polymerization share initiator, reversible addition-fracture chain transfer agents is dissolved in solvent, and logical nitrogen is removed oxygen, after 50～120 ℃ of reaction 1～24h, polymkeric substance is precipitated in methyl alcohol, then filter, be dried the rosinyl polymkeric substance that obtains different molecular weight; Described rosinyl monomer is DAE, DAME, DAB, DAA or DAMA, and structural formula is
it is Diisopropyl azodicarboxylate, benzoyl peroxide, ammonium persulphate that described radical polymerization share initiator, the one in Potassium Persulphate; Described reversible addition-fracture chain transfer agents is dithiobenzoic acid isopropyl phenyl ester, dithio benzyl benzoate, dithio toluylic acid isopropyl phenyl ester, dithiobenzoic acid-1-ethoxycarbonyl-n-propyl, two Benzyl base trithiocarbonate, S, the one in S '-bis-(ɑ-methyl phenyl ketone) trithiocarbonate.
2. the preparation method of rosin-based regular polymers as claimed in claim 1, it is characterized in that, described rosinyl monomer, reversible addition-fracture chain transfer agents and radical polymerization share initiator according to mol ratio rosinyl monomer: reversible addition-fracture chain transfer agents: radical polymerization share initiator=(2000～20): 1:(1～0.1) ratio use.
3. the preparation method of rosin-based regular polymers as claimed in claim 1, is characterized in that, described solvent is tetrahydrofuran (THF) or toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110300950.2A CN102432722B (en) | 2011-10-09 | 2011-10-09 | Method for preparing rosin-based regular polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110300950.2A CN102432722B (en) | 2011-10-09 | 2011-10-09 | Method for preparing rosin-based regular polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102432722A CN102432722A (en) | 2012-05-02 |
| CN102432722B true CN102432722B (en) | 2014-05-14 |
Family
ID=45981105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110300950.2A Expired - Fee Related CN102432722B (en) | 2011-10-09 | 2011-10-09 | Method for preparing rosin-based regular polymers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102432722B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070061A (en) * | 2016-11-15 | 2018-05-25 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of rosin and its derivative group block copolymer miniemulsion |
| CN110790905B (en) * | 2019-11-06 | 2021-12-24 | 河北工业大学 | Organic two-dimensional material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5264481A (en) * | 1991-11-22 | 1993-11-23 | Westvaco Corporation | Hydroxyacrylic modified inks |
| CN101050260A (en) * | 2007-04-14 | 2007-10-10 | 广西民族大学 | High polymer with self-crosslinked functional radicle and preparation method |
| CN101215445B (en) * | 2007-12-28 | 2011-03-16 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives allyl ester |
| US8569427B2 (en) * | 2009-10-08 | 2013-10-29 | University Of South Carolina | Polymers derived from rosin and their methods of preparation |
| CN101768240B (en) * | 2010-01-26 | 2014-04-30 | 广西民族大学 | Abietyl-containing terpolymer and preparation method thereof |
-
2011
- 2011-10-09 CN CN201110300950.2A patent/CN102432722B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102432722A (en) | 2012-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ratcliffe et al. | From a water-immiscible monomer to block copolymer nano-objects via a one-pot RAFT aqueous dispersion polymerization formulation | |
| US9109086B2 (en) | Polymers derived from rosin and their methods of preparation | |
| CN102010491B (en) | Method for preparing methacrylic acid dimethylamino ethyl ester-butyl acrylate copolymer | |
| Barner et al. | Complex molecular architecture polymers via RAFT | |
| CN103167920A (en) | Process for producing silver nanowires and agent for controlling growth of silver nanowires | |
| CN102838709B (en) | Atom transferred free radical precipitation polymerization method prepares monodispersed polymer microsphere resin | |
| CN102391413B (en) | Side chain functional polymer and preparation method thereof | |
| CN103694379B (en) | A kind of have di-block copolymer of light and pH response characteristic and preparation method thereof | |
| CN102432722B (en) | Method for preparing rosin-based regular polymers | |
| CN104592464A (en) | Organic and inorganic hybrid block copolymer containing POSS (polyhedral oligomeric silsesquioxane) and zwitter-ion structure and synthesis method of organic and inorganic hybrid block copolymer | |
| US20100331514A1 (en) | Ph-sensitive polyethylene oxide co-polymer and synthetic method thereof | |
| KR20070029629A (en) | Polymers based on n,n-diallylamine derivatives, their production and use | |
| CN107722169B (en) | Macromolecular chain transfer agent containing coumarin fluorescent group and preparation method thereof | |
| CN102304207A (en) | Method for preparing butylbenzene block copolymer core-shell emulsion through active radical miniemulsion polymerization | |
| CN104031214A (en) | St/MAH-g-MMA (styrene/maleic anhydride-grafted-methyl methacrylate) graft copolymer, and preparation method and application thereof | |
| CN104151461B (en) | Based on the polymethylmethacrylate synthesis method of continuous production soap-free polymerization thing emulsion | |
| US10611860B2 (en) | Process for preparing branched polymer via emulsion polymerization at room temperature | |
| US7732549B2 (en) | Multi-branched polymer | |
| Fleet et al. | Synthesis of novel glycopolymer brushes via a combination of RAFT-mediated polymerisation and ATRP | |
| CN111363083B (en) | Method for preparing branched polyhydroxyethyl methacrylate at room temperature by inverse emulsion polymerization | |
| CN111410612B (en) | Reducing agent monomer for preparing styrene-acrylic emulsion through oxidation reduction at normal temperature and synthetic method thereof | |
| CN102936305A (en) | Method for preparing branched polymer through suspension polymerization | |
| CN105218715A (en) | A kind of by the assorted thioketones of aromatic ring-shaped sulphur (oxygen) and derivative thereof and radical initiator and active free radical polymerization method | |
| CN114656603A (en) | Preparation method of water-soluble polymer with branched structure | |
| CN109503783A (en) | A kind of terminal siloxane modified polyacrylate block copolymer and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140514 Termination date: 20141009 |
|
| EXPY | Termination of patent right or utility model |