CN114044839A - Preparation method of controllable/active polymerization chain transfer agent and polyacrylamide with molecular weight of 100-500 ten thousand - Google Patents
Preparation method of controllable/active polymerization chain transfer agent and polyacrylamide with molecular weight of 100-500 ten thousand Download PDFInfo
- Publication number
- CN114044839A CN114044839A CN202111393694.6A CN202111393694A CN114044839A CN 114044839 A CN114044839 A CN 114044839A CN 202111393694 A CN202111393694 A CN 202111393694A CN 114044839 A CN114044839 A CN 114044839A
- Authority
- CN
- China
- Prior art keywords
- transfer agent
- polyacrylamide
- chain transfer
- molecular weight
- thousand
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to the technical field of organic synthesis and polymer synthesis, and particularly discloses a controllable/active polymerization chain transfer agent and a preparation method of polyacrylamide with the molecular weight of 100-500 ten thousand, wherein the transfer agent is 1, 4-benzyl trithiocarbonate dipropionic acid, and the structural formula of the transfer agent is 1, 4-benzyl trithiocarbonate dipropionic acid
Under a certain temperature condition, the chain transfer agent and the azodiisobutyl amidine hydrochloride (V50) initiate free radical active polymerization to synthesize polyacrylamide with narrow distribution and molecular weight of 100-500 ten thousand.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and polymer synthesis, and particularly relates to a controllable/active polymerization chain transfer agent and a preparation method of narrow-distribution polyacrylamide with molecular weight of 100-500 ten thousand.
Background
Polyacrylamide (PAM) is a water-soluble polymer material with extremely wide application, which is prepared by polymerizing an Acrylamide (AM) monomer through free radicals, and has good adsorbability, high viscosity and crosslinking property, and is widely applied to various fields of paper making, textiles, medicines, buildings, petroleum, geology, agriculture, mining oil extraction, environmental protection and the like.
PAM free radical aqueous solution polymerization can realize high monomer conversion rate and high molecular weight synthesis. However, the heat of reaction is difficult to remove and the reaction process is difficult to control, resulting in a PAM with a broad molecular weight distribution. In recent years, active/controllable radical polymerization has been developed sufficiently, and compared with traditional radical polymerization, the method can better realize control of molecular structure, is an important means for realizing molecular design and synthesis of polymers with specific structure and performance, and mainly comprises Atom Transfer Radical Polymerization (ATRP), nitrogen-oxygen stable radical polymerization (NMP), reversible addition-fragmentation-chain transfer polymerization (RAFT). The reversible addition-cracking-chain transfer polymerization has the outstanding advantages of wide monomer applicability, wide applicable reaction system (water and organic system) and strong molecular design capability, and can be used for preparing block, branched, hyperbranched and star-shaped high polymers; but still difficult to synthesize for polyacrylamide with higher molecular weight and narrower distribution. The synthesis of narrow-distribution polyacrylamide in the prior art is carried out on copper (I) chloride and tris (2-dimethylaminoethyl) amine (CuCl/Me)6TREN) by ATRP polymerization to give a molecular weight of less than 4X 105g/mol narrow distribution polyacrylamide, but the molecular weight of the polyacrylamide synthesized by the method is very small; also, a low molecular weight hydrophilic macromolecular chain transfer agent was synthesized by xanthate (MADIX)/RAFT polymerization, and then living polymerization was performed again to obtain only the highest molecular weight of 1.0X 106g/mol polyacrylamide (Read, E., Guinaudeau, A., Wilson, D.J., Cadix, A., Violleleau, F.and Destarac, M., Polym.Chem.,2014,5:2202),and the polymerization reaction is complicated to operate. In summary, narrow distribution polyacrylamide is limited to low molecular weight synthesis, and polyacrylamide with higher molecular weight and narrower distribution needs to be further developed. Aiming at the defects in the prior art, the invention provides a novel controllable/active polymerization chain transfer agent, and synthesizes polyacrylamide with narrow distribution and molecular weight of 100-500 ten thousand.
Disclosure of Invention
The invention aims to provide a controllable/active polymerization chain transfer agent and a preparation method of narrow-distribution polyacrylamide with molecular weight of 100-500 ten thousand.
In order to achieve the purpose, the invention adopts the technical scheme that:
a controllable/active polymerization chain transfer agent is 1, 4-benzyl trithiocarbonate dipropionic acid, and its structural formula is
A method for preparing a controlled/active polymeric chain transfer agent, comprising the steps of:
(1) adding mercaptopropionic acid and tripotassium phosphate into a container containing acetone, and dropwise adding CS at 0 deg.C2；
(2) Continuing to react for 0.5h at room temperature, then adding p-dibromide benzyl, reacting for 2h, and filtering to obtain yellow solid;
(3) dissolving the obtained yellow solid with distilled water, adding dilute hydrochloric acid for acidification, filtering the separated yellow solid matter under reduced pressure to obtain a crude target product, dissolving the target product with DMF, adding distilled water, filtering under reduced pressure, and drying in vacuum to obtain a purified target product; in the reaction step, the carboxylate is dissolved by the distilled water, the carboxylate is converted into carboxylic acid after being acidified by adding hydrochloric acid, the carboxylic acid is insoluble in the distilled water and can generate precipitate, and the yellow solid obtained by filtering is the target product.
The specific chemical reaction equation is as follows:
further, the mass ratio of the mercaptopropionic acid to the tripotassium phosphate to the carbon disulfide to the dibromobenzyl is 4:8:5: 3.
A method for preparing narrow-distribution medium molecular weight polyacrylamide by using a controllable/active polymerization chain transfer agent comprises the following steps: at 70 ℃, 1, 4-benzyl trithiocarbonate dipropionic acid is taken as a chain transfer agent, V50 is taken as a free radical initiator, acrylamide is taken as a monomer to react in deionized water, polyacrylamide with narrow distribution and molecular weight of 100-500 ten thousand is synthesized, and the PDI dispersion coefficient of the prepared polyacrylamide is less than 1.1.
Further, the feeding ratio of the monomer/chain transfer agent/initiator is 10000-75000: 1:0.8, and the polymerization reaction is carried out in a Schlenk bottle under the protection of vacuum nitrogen and in a 70 ℃ water bath for 6 hours.
The chemical reaction equation of the polymerization reaction is as follows:
the novel chain transfer agent provided by the invention has the advantages of simple chemical structure, few synthesis steps, simple post-treatment, reaction yield of 72.5 percent and good controllable activity polymerization reaction activity. The chain transfer agent is introduced into the synthesis of polyacrylamide, and free radical polymerization reaction is completed through a reversible addition-fragmentation chain transfer way, and the chain transfer agent has a trithioester structure and a strong electroabsorption group, so that the chain transfer agent has good free radical addition activity and a large chain transfer constant, the controllable active polymerization reaction of the polyacrylamide can be efficiently initiated, the problem that the traditional free radical polymerization reaction is uncontrollable is solved, and the obtained polyacrylamide has high molecular weight and narrow molecular weight distribution. The obtained narrow-distribution polyacrylamide can be used as a GPC standard sample of polyacrylamide and polymers similar to the polyacrylamide in structure, and can also be used as a GPC standard sample of other types of water-soluble polymers.
Drawings
FIG. 1 is 1, 4-benzyltrithiolProcess for preparing carbonic ester dipropionic acid1H NMR (DMSO-D6, 400MHz) chart.
FIG. 2 is a schematic representation of 1, 4-benzyl trithiocarbonate dipropionic acid13C NMR (DMSO-D6, 100MHz) chart.
FIG. 3 is a drawing showing 1, 4-benzyltrithiocarbonate-dipropionic acid of polyacrylamide1H NMR(D2O, 400 MHz).
Detailed Description
The controllable/active polymerization chain transfer agent and the preparation method thereof are as follows: the transfer agent is 1, 4-benzyl trithiocarbonate dipropionic acid, and the structural formula is
The reaction equation for synthesizing the controllable/active polymerization chain transfer agent is as follows:
the specific synthetic steps are as follows: 2.0g mercaptopropionic acid and 4.0g tripotassium phosphate were added to a 100ml round-bottom flask containing 40ml acetone, and 2ml CS was added dropwise at 0 deg.C2(2.5g), continuously reacting for 0.5h at room temperature, then adding 1.5g of p-dibromide benzyl, reacting for 2h, filtering to obtain a yellow solid, dissolving the yellow solid with 500ml of distilled water, adding dilute hydrochloric acid for acidification to obtain a yellow solid, namely a target product, dissolving the product with a proper amount of DMF, adding distilled water for precipitation, filtering under reduced pressure, and drying in vacuum to obtain a pure product, namely 3.18g of 1, 4-benzyl trithiocarbonate dipropionic acid.
The polymerization reaction is carried out at 70 ℃, 1, 4-benzyl trithiocarbonate dipropionic acid is taken as a chain transfer agent, V50 is taken as a free radical initiator to carry out acrylamide polymerization reaction, a 100ml Schlenk bottle is used for carrying out the reaction, the reaction bottle is vacuumized and fully degassed, and the reaction is carried out under the protection of nitrogen. The molecular weight and distribution of polyacrylamide are measured by gel permeation chromatography-18 angle laser scattering instrument.
Example 1
7.1g of acrylamide monomer, 1, 4-benzylTrithiocarbonate-dipropionic acid and initiator V50 were dissolved in 25ml of deionized water to give a ratio of [ M]0：[CTA]0：[I]010000:1:0.8, adding into a schleck bottle with a stirrer, vacuumizing, and introducing high-purity nitrogen into the reaction liquid for fully degassing. The reaction flask was placed in a 70 ℃ reaction bath and reacted for 6 hours under nitrogen protection. After the reaction is finished, adding a proper amount of water to properly dilute PAM, then adding the PAM into a large amount of methanol solution, filtering the solution under reduced pressure to obtain white solid, and drying the white solid in vacuum to obtain the polyacrylamide PAM-1, Mw110.3 ten thousand, PDI 1.087.
Example 2
7.1g of acrylamide monomer, 1, 4-benzyltrithiocarbonate dipropionic acid and initiator V50 were dissolved in 25ml of deionized water to obtain a ratio [ M [ ]]0：[CTA]0：[I]0Adding into Schlenk bottle with stirrer at 15000:1:0.8, vacuumizing, and introducing high-purity nitrogen gas to fully degas the reaction solution. The reaction flask was placed in a 70 ℃ reaction bath and reacted for 6 hours under nitrogen protection. After the reaction is finished, adding a proper amount of water to properly dilute PAM, then dropwise adding the PAM into a large amount of methanol solution, carrying out reduced pressure filtration to obtain a white solid, and carrying out vacuum drying to obtain the polyacrylamide PAM-2, Mw152.1 ten thousand, PDI 1.065.
Example 3
7.1g of acrylamide monomer, 1, 4-benzyltrithiocarbonate dipropionic acid and initiator V50 were dissolved in 25ml of deionized water to obtain a ratio [ M [ ]]0：[CTA]0：[I]025000:1:0.8, adding into a Schlenk bottle with a stirrer, vacuumizing, and introducing high-purity nitrogen into the reaction liquid for fully degassing. The reaction flask was placed in a 70 ℃ reaction bath and reacted for 6 hours under nitrogen protection. After the reaction is finished, adding a proper amount of water to properly dilute PAM, then dropwise adding the PAM into a large amount of methanol solution, carrying out reduced pressure filtration to obtain a white solid, and carrying out vacuum drying to obtain polyacrylamide PAM-3, Mw204.4 ten thousand, PDI 1.045.
Example 4
7.1g of acrylamide monomer, 1, 4-benzyl trithiocarbonate dipropionic acid and initiatorThe agent V50 was dissolved in 25ml of deionized water to give a ratio [ M]0：[CTA]0：[I]0Adding the mixture into a Schlenk bottle with a stirrer, vacuumizing, and introducing high-purity nitrogen to fully degas the reaction liquid. The reaction flask was placed in a 70 ℃ reaction bath and reacted for 6 hours under nitrogen protection. After the reaction is finished, adding a proper amount of water to properly dilute PAM, then dropwise adding the PAM into a large amount of methanol solution, carrying out reduced pressure filtration to obtain a white solid, and carrying out vacuum drying to obtain polyacrylamide PAM-4, Mw266.4 ten thousand, PDI 1.069.
Example 5
7.1g of acrylamide monomer, 1, 4-benzyltrithiocarbonate dipropionic acid and initiator V50 were dissolved in 25ml of deionized water to obtain a ratio [ M [ ]]0：[CTA]0：[I]0Adding the mixture into a Schlenk bottle with a stirrer, vacuumizing, and introducing high-purity nitrogen to fully degas the reaction liquid. The reaction flask was placed in a 70 ℃ reaction bath and reacted for 6 hours under nitrogen protection. After the reaction is finished, adding a proper amount of water to properly dilute PAM, then dropwise adding the PAM into a large amount of methanol solution, carrying out reduced pressure filtration to obtain a white solid, and carrying out vacuum drying to obtain polyacrylamide PAM-5, Mw337.8 ten thousand, PDI 1.039.
Example 6
7.1g of acrylamide monomer, 1, 4-benzyltrithiocarbonate dipropionic acid and initiator V50 were dissolved in 25ml of deionized water to obtain a ratio [ M [ ]]0：[CTA]0：[I]0Adding into Schlenk bottle with stirrer, vacuumizing, and degassing with high-purity nitrogen gas. The reaction flask was placed in a 70 ℃ reaction bath and reacted for 6 hours under nitrogen protection. After the reaction is finished, adding a proper amount of water to properly dilute PAM, then dropwise adding the PAM into a large amount of methanol solution, carrying out reduced pressure filtration to obtain a white solid, and carrying out vacuum drying to obtain polyacrylamide PAM-6, Mw408.0 ten thousand, PDI 1.062.
Example 7
7.1g of acrylamide monomer, 1, 4-benzyltrithiocarbonate dipropionic acid and initiator V50 were dissolved in 25ml of deionized waterColumn ratio is [ M ]]0：[CTA]0：[I]060000:1:0.8, the reaction mixture was added to a Schlenk flask with a stirrer, vacuum was applied, and the reaction mixture was degassed thoroughly with high-purity nitrogen. The reaction flask was placed in a 70 ℃ reaction bath and reacted for 6 hours under nitrogen protection. After the reaction is finished, adding a proper amount of water to properly dilute PAM, then adding the PAM into a large amount of methanol solution, filtering the solution under reduced pressure to obtain white solid, and drying the white solid in vacuum to obtain polyacrylamide PAM-7, Mw489.9 ten thousand, PDI 1.011.
Example 8
7.1g of acrylamide monomer, 1, 4-benzyltrithiocarbonate dipropionic acid and initiator V50 were dissolved in 25ml of deionized water to obtain a ratio [ M [ ]]0：[CTA]0：[I]070000:1:0.8, adding into Schlenk bottle with stirrer, vacuumizing, and degassing with high-purity nitrogen gas. The reaction flask was placed in a 70 ℃ reaction bath and reacted for 6 hours under nitrogen protection. After the reaction is finished, adding a proper amount of water to properly dilute PAM, then dropwise adding the PAM into a large amount of methanol solution, carrying out reduced pressure filtration to obtain a white solid, and carrying out vacuum drying to obtain polyacrylamide PAM-8, Mw500.7 ten thousand, PDI 1.010.
Example 9
7.1g of acrylamide monomer, 1, 4-benzyltrithiocarbonate dipropionic acid and initiator V50 were dissolved in 25ml of deionized water to obtain a ratio [ M [ ]]0：[CTA]0：[I]075000:1:0.8, adding into Schlenk bottle with stirrer, vacuumizing, and degassing with high-purity nitrogen gas. The reaction flask was placed in a 70 ℃ reaction bath and reacted for 6 hours under nitrogen protection. After the reaction is finished, adding a proper amount of water to properly dilute PAM, then dropwise adding the PAM into a large amount of methanol solution, carrying out reduced pressure filtration to obtain a white solid, and carrying out vacuum drying to obtain polyacrylamide PAM-9, Mw531.6 ten thousand, PDI 1.016.
Claims (5)
1. A controlled/living polymeric chain transfer agent characterized by: the transfer agent is 1, 4-benzyl trithiocarbonate dipropionic acid, and the structural formula is
2. A method for preparing a controlled/active polymerization chain transfer agent, comprising the steps of:
(1) adding mercaptopropionic acid and tripotassium phosphate into a container containing acetone, and dropwise adding CS at 0 deg.C2；
(2) Continuing to react for 0.5h at room temperature, then adding p-dibromide benzyl, reacting for 2h, and filtering to obtain yellow solid;
(3) dissolving the obtained yellow solid with distilled water, adding dilute hydrochloric acid for acidification, filtering the separated yellow solid matter under reduced pressure to obtain a crude target product, dissolving the target product with DMF, adding distilled water, filtering under reduced pressure, and drying in vacuum to obtain a purified target product.
3. The method of preparing a controlled/active polymeric chain transfer agent according to claim 2, wherein: the mass ratio of the mercaptopropionic acid to the tripotassium phosphate to the carbon disulfide to the dibromobenzyl is 4:8:5: 3.
4. The method for preparing polyacrylamide with narrow distribution and molecular weight of 100-500 ten thousand by using the controllable/active polymerization chain transfer agent as defined in claim 1, which is characterized by comprising the following steps: at 70 ℃, 1, 4-benzyl trithiocarbonate dipropionic acid is taken as a chain transfer agent, V50 is taken as a free radical initiator, acrylamide is taken as a monomer to react in deionized water, polyacrylamide with narrow distribution and molecular weight of 100-500 ten thousand is synthesized, and the PDI dispersion coefficient of the prepared polyacrylamide is less than 1.1.
5. The method for preparing polyacrylamide with narrow distribution and molecular weight of 100-500 ten thousand as claimed in claim 4, wherein: the feeding ratio of the monomer/chain transfer agent/initiator is 10000-75000: 1:0.8, and the polymerization reaction is carried out in a Schlenk bottle under the protection of vacuum nitrogen in a 70 ℃ water bath for 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111393694.6A CN114044839B (en) | 2021-11-23 | 2021-11-23 | Preparation method of controllable/active polymerization chain transfer agent and polyacrylamide with molecular weight of 100-500 ten thousand |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111393694.6A CN114044839B (en) | 2021-11-23 | 2021-11-23 | Preparation method of controllable/active polymerization chain transfer agent and polyacrylamide with molecular weight of 100-500 ten thousand |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114044839A true CN114044839A (en) | 2022-02-15 |
| CN114044839B CN114044839B (en) | 2023-08-22 |
Family
ID=80210420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111393694.6A Active CN114044839B (en) | 2021-11-23 | 2021-11-23 | Preparation method of controllable/active polymerization chain transfer agent and polyacrylamide with molecular weight of 100-500 ten thousand |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114044839B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368523B (en) * | 2022-09-19 | 2024-03-19 | 安徽农业大学 | Multi-block thermoplastic elastomer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867736A (en) * | 2019-03-15 | 2019-06-11 | 重庆科技学院 | A kind of Reversible Addition Fragmentation Chain Transfer reagent and its preparation method and application |
-
2021
- 2021-11-23 CN CN202111393694.6A patent/CN114044839B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867736A (en) * | 2019-03-15 | 2019-06-11 | 重庆科技学院 | A kind of Reversible Addition Fragmentation Chain Transfer reagent and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| RACHEL K. O\'REILLY ET AL.: "Mild and Facile Synthesis of Multi-Functional RAFT Chain Transfer Agents" * |
| 张彦昌等: "苄基三硫代碳酸酯基丙酸的合成研究" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368523B (en) * | 2022-09-19 | 2024-03-19 | 安徽农业大学 | Multi-block thermoplastic elastomer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114044839B (en) | 2023-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Water soluble hyperbranched polymers from controlled radical homopolymerization of PEG diacrylate | |
| US4777219A (en) | Carboxylate containing modified acrylamide polymers | |
| CN114044839B (en) | Preparation method of controllable/active polymerization chain transfer agent and polyacrylamide with molecular weight of 100-500 ten thousand | |
| Ali et al. | Polymerization of functionalized diallyl quaternary ammonium salt to poly (ampholyte–electrolyte) | |
| US8420771B2 (en) | PH-sensitive polyethylene oxide co-polymer and synthetic method thereof | |
| CN107722169B (en) | Macromolecular chain transfer agent containing coumarin fluorescent group and preparation method thereof | |
| CN112961278A (en) | Functionalized vinyl pyrrolidone copolymer and preparation method thereof | |
| CN110981774A (en) | Preparation method of RAFT (reversible addition-fragmentation chain transfer) agent with good water solubility | |
| CN109400868B (en) | Synthesis method of polyethylene glycol mono-anisole compound | |
| CN111527113B (en) | Process for preparing polymers containing 2-cyanoethyl groups | |
| KR101466479B1 (en) | Synthetic method of poly(vinyl acetate) using atom transfer radical polymerization and thㅝ product thereof | |
| CN108017738B (en) | Environment-friendly aqueous composite terminator | |
| Yu et al. | One-pot synthesis of hyperbranched poly (amido amine) clicked with a sugar shell via Michael addition polymerization and thiol click reaction | |
| CN113621114B (en) | Amphiphilic block copolymer worm-like micelle and preparation method and application thereof | |
| CN106905481A (en) | A kind of method for preparing functionalization DCPD Petropols | |
| CN114957572B (en) | Imine bond modified quaternary ammonium salt amphiphilic block polymer and preparation method and application thereof | |
| EP0237132B1 (en) | Process for the preparation of water-soluble saccharide polymers | |
| CN110804115B (en) | Temperature-sensitive curcumin controlled-release material and preparation method thereof | |
| CN114874112B (en) | Surface active monomer containing sodium sulfonate group, and preparation method and application thereof | |
| CN102286112A (en) | Method for polymerizing controllable/active free radicals of water-soluble monomers | |
| CN115651188B (en) | RAFT chain transfer agent and preparation method and application thereof | |
| CN108217613B (en) | A method of it catalyzes and synthesizes and prepares linear polydichlorophosphazenes | |
| US5122574A (en) | Polymerization of cis-5,6-bis(trimethylsiloxy)-1,3-cyclohexadiene and other substituted cyclohexadienes | |
| EP0180262A2 (en) | A process for the preparation of water soluble vinyl saccharide polymers. | |
| US5103057A (en) | Acrylamide copolymers containing (meth)acrylamide benzene dicarboxylic units |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |