CN111233680A - Acrylic acid biquaternary ammonium salt monomer and preparation method thereof - Google Patents

Acrylic acid biquaternary ammonium salt monomer and preparation method thereof Download PDF

Info

Publication number
CN111233680A
CN111233680A CN202010125810.5A CN202010125810A CN111233680A CN 111233680 A CN111233680 A CN 111233680A CN 202010125810 A CN202010125810 A CN 202010125810A CN 111233680 A CN111233680 A CN 111233680A
Authority
CN
China
Prior art keywords
raw material
acrylate monomer
ammonium acrylate
intermediate product
ammonium salt
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.)
Pending
Application number
CN202010125810.5A
Other languages
Chinese (zh)
Inventor
张怡
王冬梅
李天仚
谢亚雄
曹金丽
赵献增
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
High and New Technology Research Center of Henan Academy of Sciences
Original Assignee
High and New Technology Research Center of Henan Academy of Sciences
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by High and New Technology Research Center of Henan Academy of Sciences filed Critical High and New Technology Research Center of Henan Academy of Sciences
Publication of CN111233680A publication Critical patent/CN111233680A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention belongs to the technical field of biquaternary ammonium salt, and particularly relates to a biquaternary ammonium acrylate monomer and a preparation method thereof, wherein the structural general formula of the biquaternary ammonium acrylate monomer is shown in figure 3, and the preparation method of the biquaternary ammonium acrylate monomer comprises the following steps: (1) dissolving a raw material I and a raw material II in a first organic solvent, adding a catalyst, reacting for 24-72h at 60-90 ℃, and purifying to obtain an intermediate product 1; the molar ratio of the raw material I to the raw material II is 1.0: 2.0-3.6; (2) dissolving the intermediate product 1 in a second organic solvent, adding a neutralizing agent and a raw material III, reacting at 0-50 ℃ for 6-36h, and purifying to obtain the acrylic acid bis-quaternary ammonium salt monomer, wherein the molar ratio of the intermediate product 1, the raw material III and the neutralizing agent is 1.0: 1.0-1.5.

Description

Acrylic acid biquaternary ammonium salt monomer and preparation method thereof
Technical Field
The invention belongs to the technical field of biquaternary ammonium salt, and particularly relates to a biquaternary ammonium acrylate monomer and a preparation method thereof.
Background
The concept of Gemini (Gemini) was first proposed since 1991 by Menger and Littau [ Menger FM, Littau C.Gemini-surfactants: synthesis and properties.J. Am Chem Soc.1991; 113:1451-2 ], figuratively representing the structural features of such surfactants, later studies extended it to a class of surfactants formed by ionic polar head groups of two amphiphilic molecules through linking groups (spacers) with 2-3 orders of magnitude higher surface activity than the mono-quaternary ammonium salts [ Tan H, Xiao H. synthesis and antibacterial catalysis of novel-lysine geminized surfactants branched with reactive groups.tetrahedron Lett.2008; 49:1759-61 ], and has better antibacterial performance. Under the environment that the safety and health consciousness of people is continuously enhanced, the antibacterial material has attracted people's extensive attention, and the quaternary ammonium salt is introduced into the polymer, so that the polymer can be endowed with good antibacterial performance. For example, Chinese patent CN103923267B, the method introduces single quaternary ammonium salt into polyester modified acrylic resin, and endows the resin with good antibacterial performance. However, most of the double bond-containing quaternary ammonium salts that can be introduced into polymers at present are monoquaternary ammonium salts, such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N-dimethylallylamine, vinylimidazole, etc., and the double bond-containing diquaternary ammonium salts that can be introduced into polymers are less in structural variety and are more complicated in structure and preparation method, for example, chinese patent CN101343242A, which synthesizes double bond-containing diquaternary ammonium salt monomers by four-step reaction using haloalkylamine (or haloalkyl alcohol), fatty acid chloride, N' -tetramethyldiaminofatty acid ester, alkyldiamine (or in hydroxyalkylamine), and acryloyl halide (alkyl acryloyl halide) as raw materials, and thus, further improvement is required in the prior art.
Disclosure of Invention
The invention aims to provide an acrylic acid biquaternary ammonium salt monomer with good surface activity and antibacterial property and a preparation method thereof.
Based on the purpose, the invention adopts the following technical scheme:
a biquaternary ammonium acrylate monomer has a structural general formula:
Figure BDA0002394349930000011
said R0Is H or CmH2m+1Wherein m is 1-3; r1And R2Are all CnH2n+1Wherein n is 1-16; r and t are 1-4, and X is Cl, Br or I.
A method for preparing the acrylic acid biquaternary ammonium salt monomer comprises the following steps:
(1) dissolving a raw material I and a raw material II in a first organic solvent, adding a catalyst, reacting for 24-72h at 60-90 ℃, and purifying to obtain an intermediate product 1;
the molar ratio of the raw material I to the raw material II is 1.0: 2.0-3.6;
(2) dissolving the intermediate product 1 in a second organic solvent, adding a neutralizing agent and a raw material III, reacting for 6-36h at 0-50 ℃, and purifying to obtain an acrylic acid bis-quaternary ammonium salt monomer; the mol ratio of the intermediate product 1, the raw material III and the neutralizing agent is 1.0: 1.0-1.5.
The chemical formula of the raw material IIs composed of
Figure BDA0002394349930000021
Wherein X is Cl, Br or I, and r and t are integers of 1-4;
the chemical formula of the raw material II is
Figure BDA0002394349930000022
Wherein n is 1-16;
the chemical formula of the raw material III is
Figure BDA0002394349930000023
Wherein R is0Is CmH2m+1，m＝1-3；
The chemical formula of the intermediate product 1 is as follows:
Figure BDA0002394349930000024
wherein X is Cl, Br or I, and r and t are integers of 1-4; r1And R2Are all CnH2n+1，n＝1-16。
Further, the raw material I is 1, 3-dichloro-2-propanol.
Further, the raw material II is any one of N, N-dimethyl N-octylamine, N-dimethyl decylamine, N-dimethyl dodecyl tertiary amine and hexadecyl dimethyl tertiary amine.
Further, the raw material III is methacryloyl chloride or acryloyl chloride.
Further, the first organic solvent is at least one of methanol, ethanol, isopropanol, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane and dimethyl sulfoxide.
Further, the second organic solvent is at least one of methanol, ethanol, ethyl acetate, chloroform or dichloromethane.
Further, the neutralizing agent is at least one of triethylamine, potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide.
Further, the catalyst is potassium iodide and/or sodium iodide.
The acrylic acid biquaternary ammonium salt monomer prepared by the invention contains double bonds, has simple chemical structure, good reaction activity and high surface activity, can be introduced into a polymer by self-polymerization or copolymerization, and the reaction process is easy to control, so that the obtained polymer has good surface activity and antibacterial performance. The raw materials used in the method for preparing the acrylic acid biquaternary ammonium salt monomer are the existing industrial raw materials, the reaction steps are few (two-step reaction), the post-treatment is simple, the reaction process is easy to control, the reaction yield is high, and the large-scale production is convenient.
Drawings
FIG. 1 is a NMR chart of examples 1-4;
FIG. 2 is a Fourier transform infrared spectrum of examples 1-4;
FIG. 3 shows the general structural formula of the acrylic acid bis-quaternary ammonium salt monomer.
Detailed Description
The structure of the diquaternary ammonium acrylate monomer obtained in the following examples 1-4 is shown as follows, and is respectively represented by AGEN, wherein n is the number of carbon atoms in long hydrophobic alkyl chain, and R is0Is H:
Figure BDA0002394349930000031
example 1:
dissolving 1, 3-dichloro-2-propanol and N, N-dimethyl N-octylamine in ethanol at a molar ratio of 1.0: 2.0, adding potassium iodide as catalyst, heating to 60 deg.C, reacting for 24 hr, distilling under reduced pressure to remove most of solvent, adding petroleum ether, and vacuum filtering to obtain white intermediate product; dissolving the intermediate product, methacryloyl chloride and triethylamine serving as a neutralizing agent in a molar ratio of 1.0: 1.0 in chloroform, reacting at 0 ℃ for 6 hours, washing with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated sodium chloride and deionized water in sequence, drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain the acrylic acid biquaternary ammonium salt monomer AEG 8.
Example 2:
dissolving 1, 3-dichloro-2-propanol and N, N-dimethyl decylamine in isopropanol at a molar ratio of 1.0: 2.5, adding sodium iodide as catalyst, heating to 90 deg.C, reacting for 30 hr, distilling under reduced pressure to remove most solvent, adding petroleum ether, and vacuum filtering to obtain white intermediate; dissolving the intermediate product, acryloyl chloride and neutralizing agent sodium hydroxide in a molar ratio of 1.0: 1.3 in dichloromethane, reacting at 40 ℃ for 10h, washing with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated sodium chloride and deionized water in sequence, drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain the acrylic acid biquaternary ammonium salt monomer AEG 10.
Example 3:
dissolving 1, 3-dichloro-2-propanol and N, N-dimethyl dodecyl tertiary amine in methanol at a molar ratio of 1.0: 2.8, adding sodium iodide as catalyst, heating to 70 deg.C, reacting for 48 hr, distilling under reduced pressure to remove most of solvent, adding petroleum ether, and vacuum filtering to obtain white intermediate; dissolving the intermediate product, acryloyl chloride and neutralizing agent sodium hydroxide in a molar ratio of 1.0: 1.3 in dichloromethane, reacting at 40 ℃ for 20 hours, washing with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated sodium chloride and deionized water in sequence, drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain the acrylic acid biquaternary ammonium salt monomer AEG 12.
Example 4:
dissolving 1, 3-dichloro-2-propanol and hexadecyl dimethyl tertiary amine in isopropanol at a molar ratio of 1.0: 3.6, adding potassium iodide as a catalyst, heating to 90 ℃, reacting for 72 hours, distilling under reduced pressure to remove most of the solvent, adding petroleum ether, and filtering to obtain a white intermediate product; dissolving the intermediate product, acryloyl chloride and neutralizing agent sodium hydroxide in a molar ratio of 1.0: 1.5 in dichloromethane, reacting at 50 ℃ for 36h, sequentially washing with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated sodium chloride and deionized water, drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain the acrylic acid biquaternary ammonium salt monomer AEG 16.
Test example 1:
the bis-quaternary ammonium salt monomer AEG8 prepared in examples 1-4 was subjected to NMR spectroscopy using a NMR spectrometer in DMSO-d6 as a test resultFIG. 1 shows the results of tests (1) to (4) in examples 1 to 4, respectively. Wherein 3.01ppm and 3.10ppm of H are bis-quaternary ammonium salt N in the obtained monomer+The characteristic peaks of methyl and methylene on the double bond are 5.73ppm-7.25 ppm.
Test example 2:
the infrared spectrum test of the diquaternary ammonium salt monomer AEG8 prepared in examples 1-4 was carried out, and the Fourier transform infrared spectrum test results are shown in FIG. 2, wherein the characteristic peak of the double bond (C ═ C) and the characteristic peak of the ester bond (C ═ O) were 3020cm each-1And 1725cm-1And (c) occurs.
Test example 3:
the antibacterial properties of the diquaternary ammonium acrylate monomers obtained in examples 1 to 4 were measured for Minimum Inhibitory Concentration (MIC) by reference to NCCLS standard method, and measured by 96-well plate method according to NCCLS standard, and the control was selected from the common monoquaternary ammonium salt dodecyltrimethylammonium bromide (DTAB), and the experimental strains were Escherichia coli (ATCC-25922) and Staphylococcus aureus (ATCC-6538). Adding 100 mu L of sterile MH culture medium into each well of a 96-well plate, then adding 100 mu L of diluted sample of the embodiment to be tested into the first well, diluting for 10 times, sucking 100 mu L of the sample, adding the sample into the second well, repeating the steps until the last well is reached, sucking 100 mu L of the sample into the last well, and discarding. Then 100. mu.L of diluted bacterial solution (10) was added to each well6CFU/mL). DTAB is used as a control, 3 wells are respectively added with sterile MH culture medium without bacteria liquid or samples to be used as a blank control, and 3 wells without antibacterial samples and only with bacteria liquid are used as a negative control. The 96-well plate was placed in an incubator at 37 ℃ for 16-20 hours, 5. mu.L of 5% triphenyltetrazolium chloride (TTC) was added to each well, and the results were observed after half an hour, and are shown in Table 1.
Table 1:
Figure BDA0002394349930000051
as can be seen from the data in Table 1, the antibacterial effect of the monomer prepared by the invention is much higher than that of the common quaternary ammonium salt DTAB.

Claims (9)

1. A biquaternary ammonium acrylate monomer is characterized in that the structural general formula is as follows:
Figure FDA0002394349920000011
said R0Is H or CmH2m+1Wherein m is 1-3; r1And R2Are all CnH2n+1Wherein n is 1-16; r and t are 1-4, and X is Cl, Br or I.
2. A method of making the diquaternary ammonium acrylate monomer of claim 1, comprising the steps of:
(1) dissolving a raw material I and a raw material II in a first organic solvent, adding a catalyst, reacting for 24-72h at 60-90 ℃, and purifying to obtain an intermediate product 1;
the molar ratio of the raw material I to the raw material II is 1.0: 2.0-3.6;
(2) dissolving the intermediate product 1 in a second organic solvent, adding a neutralizing agent and a raw material III, reacting for 6-36h at 0-50 ℃, and purifying to obtain an acrylic acid bis-quaternary ammonium salt monomer; the mol ratio of the intermediate product 1, the raw material III and the neutralizing agent is 1.0: 1.0-1.5.
The chemical formula of the raw material I is
Figure FDA0002394349920000012
Wherein X is Cl, Br or I, and r and t are integers of 1-4;
the chemical formula of the raw material II is
Figure FDA0002394349920000013
Wherein n is 1-16;
the chemical formula of the raw material III is
Figure FDA0002394349920000014
Wherein R is0Is CmH2m+1，m＝1-3；
Of said intermediate 1The chemical formula is:
Figure FDA0002394349920000021
wherein X is Cl, Br or I, and r and t are integers of 1-4; r1And R2Are all CnH2n+1，n＝1-16。
3. The method for preparing diquaternary ammonium acrylate monomer according to claim 2, wherein the raw material I is 1, 3-dichloro-2-propanol.
4. The method for preparing diquaternary ammonium acrylate monomer according to claim 2, wherein the raw material II is one of N, N-dimethyl N-octylamine, N-dimethyl decylamine, N-dimethyl dodecylamine and hexadecyl dimethyl tertiary amine.
5. The method for preparing the diquaternary ammonium acrylate monomer according to claim 2, wherein the raw material III is methacryloyl chloride or acryloyl chloride.
6. The method of claim 2, wherein the first organic solvent is at least one of methanol, ethanol, isopropanol, N-dimethylformamide, N-dimethylacetamide, 1, 4 dioxane and dimethylsulfoxide.
7. The method of claim 2, wherein the second organic solvent is at least one of methanol, ethanol, ethyl acetate, chloroform or dichloromethane.
8. The method for preparing diquaternary ammonium acrylate monomer according to claim 2, wherein the neutralizing agent is at least one of triethylamine, potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide.
9. The method of claim 2, wherein the catalyst is potassium iodide and/or sodium iodide.
CN202010125810.5A 2019-04-29 2020-02-27 Acrylic acid biquaternary ammonium salt monomer and preparation method thereof Pending CN111233680A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2019103531823 2019-04-29
CN201910353182 2019-04-29

Publications (1)

Publication Number Publication Date
CN111233680A true CN111233680A (en) 2020-06-05

Family

ID=70863143

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010125810.5A Pending CN111233680A (en) 2019-04-29 2020-02-27 Acrylic acid biquaternary ammonium salt monomer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111233680A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113233995A (en) * 2021-04-13 2021-08-10 华南理工大学 Antibacterial styrene-acrylic emulsion containing biquaternary ammonium salt structure and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101869813A (en) * 2009-04-23 2010-10-27 中国科学院成都有机化学有限公司 Preparation method for gemini surfactant with double bonds
CN105327653A (en) * 2015-10-14 2016-02-17 西安双子精细化工有限公司 High water solubility cationic gemini surfactant, and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101869813A (en) * 2009-04-23 2010-10-27 中国科学院成都有机化学有限公司 Preparation method for gemini surfactant with double bonds
CN105327653A (en) * 2015-10-14 2016-02-17 西安双子精细化工有限公司 High water solubility cationic gemini surfactant, and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ACS: "STN检索报告", 《STN REGISTRY》 *
HUI WANG等: "Antibacterial Activity of Geminized Amphiphilic Cationic Homopolymers", 《LANGMUIR》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113233995A (en) * 2021-04-13 2021-08-10 华南理工大学 Antibacterial styrene-acrylic emulsion containing biquaternary ammonium salt structure and preparation method and application thereof
CN113233995B (en) * 2021-04-13 2022-04-05 华南理工大学 Antibacterial styrene-acrylic emulsion containing biquaternary ammonium salt structure and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN114634495B (en) Water-soluble photosensitizer with broad-spectrum antibacterial activity and preparation method and application thereof
CN111233680A (en) Acrylic acid biquaternary ammonium salt monomer and preparation method thereof
CN108722203B (en) Preparation method of high-flux polyaniline composite nanofiltration membrane
CN113457564B (en) Esterified SMA (styrene maleic anhydride) modified quaternary ammonium/phosphonium salt high-molecular antibacterial surfactant and application thereof
CN101343242A (en) Acryloyl di-quaternary ammonium salt and preparation thereof
CN104190267A (en) Preparation method of alkylated chitosan modified PVDF (Polyvinylidene Fluoride) separation membrane
CN111116472B (en) Seven-membered cyclic lysine derivative monomer and preparation method thereof, and antibacterial poly (epsilon-lysine) derivative and preparation method thereof
WO2010118951A2 (en) Method for producing monoethylenically unsaturated glycosylamines
CN110343196B (en) Method for synthesizing diamine terminated polystyrene based on ATRP active polymerization method and application
KR101650593B1 (en) Processes for producing N-alkyl (alkyl)acrylamides
CN102784623B (en) Preparation method of non-dissolving antibacterial polyquaternium modified active carbon
CN107556210B (en) N-alkyl-N-substituted vinyl formamide compound and synthesis method thereof
CN112266426A (en) Alkylated quaternary ammonium type modified chitosan and rabbit hair fabric finishing method thereof
CN102391139B (en) Energy-saving and environmentally-friendly process for synthesizing alkyl betaine
CN108178962B (en) Amphoteric ion antifouling paint resin and preparation method thereof
CN112920324B (en) Quaternary ammonium salt polymer and preparation method and application thereof
CN112940162B (en) Synthetic method of highly-ordered dendritic heterogeneous sugar-containing polymer containing multiple glycosyl groups
CN100376550C (en) Quaternary bis-ammonium salt diamine fluoride and preparation method thereof
CN105294506B (en) A kind of guanidine radicals long-chain gemini quaternary ammonium salt and preparation method thereof
CN103709208A (en) Method for preparing glucosamine monomer
JP5024585B2 (en) Novel itaconic sugar derivative and process for producing the same
KR101331912B1 (en) O-benzoyl chitosan derivative and method for preparing the same
CN106699964B (en) A kind of anion-polyacrylamide flocculant, preparation method and applications
CN116410464B (en) Main chain cationic polymer capable of being click chemically modified and preparation method thereof
CN107245052A (en) A kind of atazanavir preparation method

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20200605

RJ01 Rejection of invention patent application after publication