CN110527084B - Biodegradable L-structure polyaspartic acid high-molecular dispersant and preparation method thereof - Google Patents
Biodegradable L-structure polyaspartic acid high-molecular dispersant and preparation method thereof Download PDFInfo
- Publication number
- CN110527084B CN110527084B CN201910391349.5A CN201910391349A CN110527084B CN 110527084 B CN110527084 B CN 110527084B CN 201910391349 A CN201910391349 A CN 201910391349A CN 110527084 B CN110527084 B CN 110527084B
- Authority
- CN
- China
- Prior art keywords
- acid
- biodegradable
- polyaspartic acid
- polyaspartic
- aspartic acid
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention relates to a biodegradable L-structure polyaspartic acid high-molecular dispersant and a preparation method thereof. The biodegradable L-structure polyaspartic acid high-molecular dispersing agent comprises L-structure aspartic acid; polycondensate: one or more of 2,4,7, 9-dimethyl-5-decyne-4, 7-diol or 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate or 3, 8-dimethyl-4, 6-decyldiyne-3, 8-diol or a-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene); catalyst: trihydroxy-diethylenediamine or tetrahydroxyethylethylenediamine THEED or organic acids; auxiliary agent: dipropyl maleate or a polymer of (Z) -2-butenedioic acid and 2-acrylic acid. The dispersion of the anode and cathode materials of the current power lithium battery, the dispersion of pigment and filler color paste of water-based paint and ink, the dispersion of silicon material of silicon columns for preparing chips, and the wetting dispersion of carbon nanotubes, high-carbon graphite, graphene and three-dimensional silicon aerogel are solved. The wetting dispersion of the cutting coolant is synergistically solved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a biodegradable L-structure polyaspartic acid high polymer dispersant and a preparation method thereof.
Background
The poly-aspartic acid is a high molecular polymer with certain relative molecular mass, wherein the same amino acid monomer is dehydrated among molecules to form amido bonds, but the poly-aspartic acid is different from proteins with specific amino acid sequences. Currently, the poly (aspartic acid) which is being researched more mainly comprises gamma polyglutamic acid which can be biosynthesized, epsilon polylysine and L-structural polyaspartic acid which is chemically polymerized. The poly-aspartic acid material has a biodegradable peptide chain structure, and a large amount of carboxyl and amino are arranged on the side chain, so the poly-aspartic acid material is widely used for biodegradable green dispersing agents, water-retaining agents and drug sustained-release carriers.
Meanwhile, the application of the polyaspartic acid in the aspects of fertilizer synergists, water retention agents and complexing agents and biological materials becomes a new research hotspot, namely, a series of polyaspartic acid functional materials with different application performances are synthesized by molecular structure design and controllable synthesis means.
Disclosure of Invention
The invention aims to provide a biodegradable L-structure polyaspartic acid high-molecular dispersing agent and a preparation method thereof, which solve the problems of dispersion of anode and cathode materials of the current power lithium battery, dispersion of pigment and filler color paste of water-based paint and ink and silicon material of silicon columns for preparing chips, and wetting and dispersion of carbon nanotubes, high-carbon graphite, graphene and three-dimensional silicon aerogel. The wetting dispersion of the cutting coolant is synergistically solved.
In order to achieve the above purpose, the invention adopts the technical scheme that: a biodegradable L-structure polyaspartic acid high molecular dispersant comprises L-structure aspartic acid;
polycondensate: one or more of 2,4,7, 9-dimethyl-5-decyne-4, 7-diol or 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate or 3, 8-dimethyl-4, 6-decyldiyne-3, 8-diol or a-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene);
catalyst: trihydroxy-diethylenediamine or tetrahydroxyethylethylenediamine THEED or organic acids;
auxiliary agent: dipropyl maleate or a polymer of (Z) -2-butenedioic acid and 2-acrylic acid.
Further, the kit also comprises a targeting carrier: polyethylene glycol methyl ether (MPEG) or polyethylene glycol (PEG) or polyethylene glycol allyl methyl ether;
furthermore, the pesticide also comprises a regulator, wherein the regulator comprises triethanolamine, an organic acid or an organic base.
More preferably, the L-structural aspartic acid is beta carbobenzoxy L-structural aspartic acid.
Further, the biodegradable L-structure polyaspartic acid high molecular dispersant comprises the following components in parts by mass: 200-450 parts of L-structure aspartic acid; 500-2000 parts of the polycondensate; 100 portions and 150 portions of the catalyst.
A preparation method of a biodegradable L-structure polyaspartic acid high molecular dispersant comprises the following steps: polymerizing L-structure aspartic acid and polycondensate in the presence of catalyst, vacuumizing at 60-80 deg.c for 2-4 hr, regulating pH value with regulator, filtering and packing.
A preparation method of a biodegradable L-structure polyaspartic acid high molecular dispersant comprises the following steps: firstly, using L-structure aspartic acid and a target carrier to pre-polymerize and sum at 40-80 ℃ to form a pre-polymerized material, then pre-polymerizing the pre-polymerized material and the target carrier under a catalyst to form a copolymer, and then carrying out polycondensation on the copolymer and a polycondensate.
Furthermore, an auxiliary agent is added in the prepolymerization process.
Further preferably, beta carbobenzoxy L-aspartic acid is first prepolymerized with polyethylene glycol allyl methyl ether at 40-80 deg.C to form L-polyaspartic acid ester, then prepolymerized with MPEG under trihydroxy diethyleneamine catalyst to form L-polyaspartic acid propenyl ester copolymer, and then the L-polyaspartic acid propenyl ester copolymer is second polycondensed with 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate +. alpha-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene).
And further, vacuumizing the product after the secondary polycondensation for 2-5 hours at the temperature of 80-120 ℃, and finally adjusting the pH value by using a regulator, filtering and packaging.
The invention has the technical effects that: the invention mainly prepares a broad-spectrum biodegradable green polymer dispersant by relying on the existing L-structure polyaspartic acid and various organic polymerization, and the biodegradable green polymer dispersant with a special structure can well solve the problems of dispersion of anode and cathode materials of the current power lithium battery, dispersion of color filler color paste of water-based paint and ink and silicon column silicon materials for preparing chips, and wetting and dispersion of carbon nanotubes, high-carbon graphite, graphene and three-dimensional silicon aerogel. The wetting dispersion of the cutting coolant is synergistically solved.
Drawings
FIG. 1 is a simple structural formula of a product obtained by the process of the present invention;
FIG. 2 is a graph showing the results of a foam inhibition experiment for products according to various examples of the present invention.
Detailed Description
The invention focuses on the innovative application of polyaspartic acid derivatives in the fields of green polymer dispersants and the like. The invention mainly relies on the existing L-structure polyaspartic acid and various organic polymerization to prepare a broad-spectrum biodegradable green high molecular dispersant, and the biodegradable green high molecular dispersant with a special structure can well solve the problems of the dispersion of anode and cathode materials of the current power lithium battery, the dispersion of color filler color paste of water-based paint and ink and silicon column silicon materials for preparing chips, and the wetting dispersion of carbon nano-tubes, high-carbon graphite, graphene and three-dimensional silicon aerogel. The wetting dispersion of the cutting coolant is synergistically solved.
The product of the invention mainly comprises the following raw materials: 1: l-structural aspartic acid, 2: polyethylene glycol methyl ether (MPEG), 3: polyethylene glycol (PEG), 4: 2,4,7, 9-dimethyl-5-decyne-4, 7-diol, 5: 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate, 6: 3, 8-dimethyl-4, 6-decanediyne-3, 8-diol, 7: a-isotridecyl- Ω -hydroxy-poly (oxy-1, 2-ethylene), 8: trihydroxy-diethyleneamine, 9: tetrahydroxyethyl ethylenediamine (tee), 10: dipropyl maleate, 11: polymers of (Z) -2-butenedioic acid and 2-acrylic acid, and the like.
The process of the invention comprises the following steps:
the invention mainly relies on the existing L-structure polyaspartic acid and various organic polymers to prepare a broad-spectrum biodegradable green high-molecular dispersant, and firstly, polyethylene glycol methyl ether (MPEG) is used as a targeting carrier. As polyethylene glycol methyl ether (MPEG) is widely used as a drug sustained release carrier, but the drug loading efficiency and stability of the polyethylene glycol methyl ether (MPEG) as the drug sustained release carrier are not high, the invention utilizes L- (structure) polyaspartic acid to research the aspects of synthesis, solution property, drug sustained release performance and the like of a block copolymer formed by the L-polyaspartic acid and the polyethylene glycol methyl ether (MPEG).
More preferably, in the invention, beta carbobenzoxy L- (structure) aspartic acid and polyethylene glycol allyl methyl ether are firstly prepolymerized at 40-80 ℃ to form L-polyaspartic acid ester, then the copolymer is prepolymerized with MPEG under the catalysis of trihydroxy diethyleneamine to form a copolymer, and then the L-polyaspartic acid allyl ester copolymer and 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate + alpha-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylidene) (i.e. isomeric C13 polyether in the following structural formula) are subjected to polycondensation to prepare the biodegradable L-polyaspartic acid allyl ester copolymer (high molecular green dispersant) containing side groups.
The simple structural formula of the obtained product is shown in figure 1.
In the present application, L-polyaspartic acid, L-structural aspartic acid, and L-polyaspartic acid all represent the same substance.
The specific formulation of the present invention, i.e., the process for producing the product, is given below:
□ formulation 1
MPEG2000:400 parts + ② L-polyaspartic acid (preferably beta carbobenzoxy L-aspartic acid): 450 parts of + trihydroxy divinylamine: 150 parts of +2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate 500 parts of +. alpha-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene): 500 portions
□ Process for preparing the product of the formula
In this example, beta carbobenzoxy L-aspartic acid was first prepolymerized with MPEG at 40-80 deg.C to form L-polyaspartic acrylate, then prepolymerized with trihydroxy diethyleneamine catalyst, and then secondary polycondensed with L-polyaspartic acrylate copolymer and 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate + A-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), which was vacuum reacted at 80-120 deg.C for 3-5 hours. Finally, triethanolamine or pH value adjustment is used for filtering and packaging, and the biodegradable L-polyaspartic allyl ester copolymer (high molecular green dispersant) containing side groups is prepared.
□ formula 2
400 portions of PEG8000:200 + beta-L-polyaspartic acid (preferably beta-carbobenzoxy L-aspartic acid): 200 + triethanolamine: 100 + 150 parts of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate, 500 + 1000 parts of ALPHA-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene): 500-1000 parts
□ Process for preparing the product of the formula
In this example, beta carbobenzoxy L-aspartic acid and PEG were first prepolymerized at 40-80 deg.C to form L-polyaspartic acrylate, then prepolymerized under triethanolamine catalyst, and then subjected to secondary polycondensation by L-polyaspartic ester copolymer and 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate + A-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene), which was vacuum-reacted at 80-120 deg.C for 3-5 hours. Finally, triethanolamine or pH value adjustment is used for filtering and packaging, and the biodegradable L-polyaspartic allyl ester copolymer (high molecular green dispersant) containing side groups is prepared.
□ formula 3
(ii) L-polyaspartic acid (preferably β benzyloxycarbonyl L-aspartic acid): 200 + 100 + 150 +2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate 500 + 1000 +. alpha-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene): 500-1000 parts
□ Process for preparing the product of the formula
In this example we polymerized beta carbobenzoxy L-aspartic acid with 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate + A-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene) in the presence of triethanolamine catalyst, which was reacted at 60- -80 ℃ for 2-4 hours under vacuum. Finally, the pH value is adjusted by organic acid or organic alkali, and the L-polyaspartic acrylic ester copolymer (macromolecular green dispersant) containing the side group, which can be biodegraded, is prepared and packaged.
Formulation 4
(ii) L-polyaspartic acid (preferably β benzyloxycarbonyl L-aspartic acid): 200 + 450 parts of organic acid: 100 plus 150 parts of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate, 500 plus 1000 parts of +, [ dipropyl maleate ]: 500-1000 parts
□ Process for preparing the product of the formula
In this example we polymerized beta carbobenzoxy L-aspartic acid with dipropyl maleate +2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate + A-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene) in the presence of an organic acid catalyst, which was subjected to vacuum at 80- -110 ℃ for 2-4 hours. Finally, the pH value is adjusted by organic acid or organic alkali, and the L-polyaspartic acrylic ester copolymer (macromolecular green dispersant) containing the side group, which can be biodegraded, is prepared and packaged.
In conclusion, the invention is not limited to the preparation of the green macromolecular dispersant by the secondary polymerization reaction of the L-polyaspartic acid and the conventional different molecular broken polyethers, and can also be compounded in a crossed manner. Is applied to the application and preparation of various high polymer material hyperbranched technologies.
The following is an application experiment report of the L-structure polyaspartic acid polymeric dispersant of the invention:
purpose of the experiment: testing the dispersing efficiency of the dispersant
Experimental equipment: high-speed grinding dispersion machine, glass plate, 500ml beaker, 10U, 25U wire rod, fineness board, electron microscope, electron laser distribution particle size instrument
Experimental materials: deionized water, titanium dioxide R-996, carbon black C111, dispersant (formula 1-4), wetting agent Surfadol:465 and defoaming agent Surfadol: A560
The experimental formula is as follows:
and (3) physical detection results:
and (4) conclusion: through multiple application experimental analysis, the L-structure polyaspartic acid high molecular dispersant products with the formulas 1 to 4 can be well applied to modification of water-based paint, ink, lithium battery anode and cathode materials and surface modification treatment of graphene materials.
Further: the addition ratio of the pigment to the dispersant is as follows:
the inorganic color filler is 10-20% of the formula of the solid pigment
The organic pigment is 50-100% of the formula ratio of the solid part of the pigment
The special oxidation modification is 20-50% of the formula ratio of the solid part of the pigment
The special nano powder material is 100-200% of the formula ratio of the solid part of the pigment.
Claims (7)
1. A biodegradable L-structure polyaspartic acid high molecular dispersant is characterized in that: including L-structural aspartic acid;
polycondensate: 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate and alpha-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene) are compounded;
catalyst: trihydroxy-diethylenediamine or tetrahydroxyethylethylenediamine THEED or organic acids;
auxiliary agent: dipropyl maleate or a polymer of (Z) -2-butenedioic acid and 2-acrylic acid;
a regulator: triethanolamine, an organic acid or an organic base;
the L-structure aspartic acid is beta carbobenzoxy L-structure aspartic acid;
the dispersing agent comprises the following components in parts by mass: 200-450 parts of L-structure aspartic acid; 500-2000 parts of the polycondensate; 100 portions and 150 portions of the catalyst.
2. The biodegradable L-structure polyaspartic acid polymeric dispersant of claim 1, which is characterized in that: also included are targeting vectors: polyethylene glycol methyl ether MPEG or polyethylene glycol PEG or polyethylene glycol allyl methyl ether.
3. The method for preparing the biodegradable L-structure polyaspartic acid polymeric dispersant according to claim 1, characterized by comprising the following steps: polymerizing L-structure aspartic acid and polycondensate in the presence of catalyst, vacuumizing at 60-80 deg.c for 2-4 hr, regulating pH value with regulator, filtering and packing.
4. The method for preparing the biodegradable L-structure polyaspartic acid polymeric dispersant according to claim 2, characterized by comprising the following steps: firstly, L-structure aspartic acid and a target carrier are prepolymerized at 40-80 ℃ to form a prepolymer, then the prepolymer and the target carrier are prepolymerized under a catalyst to form a copolymer, and then the copolymer and the polycondensate are subjected to polycondensation.
5. The method for preparing biodegradable L-structured polyaspartic acid polymeric dispersant according to claim 4, characterized in that an auxiliary agent is added during the prepolymerization.
6. The method of claim 4 or 5, wherein the biodegradable L-structural polyaspartic acid polymer dispersant is prepared by pre-polymerizing beta carbobenzoxy L-aspartic acid with polyethylene glycol allyl methyl ether at 40-80 ℃ to form L-polyaspartic acid ester, pre-polymerizing with MPEG under trihydroxy diethyleneamine catalyst to form L-polyaspartic acid allyl ester copolymer, and performing secondary polycondensation of the L-polyaspartic acid allyl ester copolymer with 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol ethoxylate + A-isotridecyl-omega-hydroxy-poly (oxy-1, 2-ethylene).
7. The method for preparing the biodegradable L-structured polyaspartic acid polymeric dispersant of claim 6, wherein the product after the secondary polycondensation is subjected to vacuum pumping reaction at 80-120 ℃ for 2-5 hours, and finally, pH value is adjusted by using a regulator, and the product is filtered and packaged.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910391349.5A CN110527084B (en) | 2019-05-12 | 2019-05-12 | Biodegradable L-structure polyaspartic acid high-molecular dispersant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910391349.5A CN110527084B (en) | 2019-05-12 | 2019-05-12 | Biodegradable L-structure polyaspartic acid high-molecular dispersant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110527084A CN110527084A (en) | 2019-12-03 |
| CN110527084B true CN110527084B (en) | 2022-01-28 |
Family
ID=68659784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910391349.5A Active CN110527084B (en) | 2019-05-12 | 2019-05-12 | Biodegradable L-structure polyaspartic acid high-molecular dispersant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110527084B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461851B (en) * | 2021-06-11 | 2022-05-20 | 华中科技大学 | Application of polymer and photoresist containing polymer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2792312B1 (en) * | 1999-04-15 | 2001-06-08 | Oreal | THIA-ALCYNOIC (POLY) COMPOUNDS AND DERIVATIVES THEREOF, COMPOSITIONS COMPRISING SAME AND THEIR USE |
| EP1950180A1 (en) * | 2007-01-25 | 2008-07-30 | GEO - Ground Engineering Operations Produtos e Solucoes de Engenharia e Geotecnia, Lda | Chemical composition and process for treating liquid dispersions |
| CN103329895A (en) * | 2013-06-04 | 2013-10-02 | 广东中迅农科股份有限公司 | Wettable powder containing new-type environmental chelating dispersants |
| CN105949987B (en) * | 2016-07-11 | 2018-07-31 | 广东遂达工程技术有限公司 | A kind of imine modified polyaspartic ester water proof anti-corrosive paint and preparation method and application |
-
2019
- 2019-05-12 CN CN201910391349.5A patent/CN110527084B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110527084A (en) | 2019-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111303368B (en) | Water-based polyaspartic acid ester resin and preparation method thereof | |
| Zhong et al. | A versatile family of degradable non-viral gene carriers based on hyperbranched poly (ester amine) s | |
| Huang et al. | One-pot synthesis and biological imaging application of an amphiphilic fluorescent copolymer via a combination of RAFT polymerization and Schiff base reaction | |
| CN110527084B (en) | Biodegradable L-structure polyaspartic acid high-molecular dispersant and preparation method thereof | |
| WO2005023899A1 (en) | Acid-sensitive polyacetals and methods | |
| Han et al. | The synthesis, deprotection and properties of poly (γ-benzyl-L-glutamate) | |
| Zeng et al. | Preparation and characterization of Poly (γ-glutamic acid) hydrogels as potential tissue engineering scaffolds | |
| CN105622932B (en) | Nano nylon microsphere and preparation method thereof | |
| CN112679709A (en) | Polyester for heat shrinkable film and preparation method thereof | |
| CN115521583B (en) | Preparation method of modified silicon dioxide and application of modified silicon dioxide in epoxy resin | |
| CN101323662A (en) | Biodegradable hyper branched aliphatic polyamide fiber daiamid and preparation thereof | |
| Poulhès et al. | Novozym 435-catalyzed synthesis of polyetheramides from amino-esters, or diesters and diamines built on ethylene-and diethylene-glycol moieties | |
| CN104987499B (en) | Water-soluble maleopimaric acid hyperbranched polyester and preparation method therefor | |
| CN105348495A (en) | Catalyst for polylactone preparation | |
| CN108003325B (en) | Preparation method of high-molecular water-based epoxy resin, resin prepared by preparation method and application of resin | |
| CN105418893A (en) | Preparation method of thermosetting resin composition and cured product thereof | |
| CN116396474B (en) | Hyperbranched polyether ester with multiple purposes and preparation method thereof | |
| CN1232565C (en) | Terminal group-adjustable superbranched polyamide and its preparation method | |
| CN114349935B (en) | Low-viscosity aqueous epoxy curing agent and preparation method thereof | |
| CN101906210B (en) | Method for synthesizing polypeptide in presence of ammonia-base rare earth catalyst | |
| CN116003787A (en) | Hyperbranched poly (beta-amino ester) containing hydrophobic alkyl chains, preparation method thereof and mRNA delivery application | |
| CN110563374B (en) | Raw material grinding aid for vertical mill and preparation method thereof | |
| EP0426383A2 (en) | High molecular weight trifunctional polyoxyethylene amines | |
| CN114195998A (en) | Process for preparing high-strength polyglycolic acid by continuous polycondensation | |
| CN101580582B (en) | Method for preparing polylactic acid |
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 |