[go: up one dir, main page]

CN112300358A - Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof - Google Patents

Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof Download PDF

Info

Publication number
CN112300358A
CN112300358A CN202010460317.9A CN202010460317A CN112300358A CN 112300358 A CN112300358 A CN 112300358A CN 202010460317 A CN202010460317 A CN 202010460317A CN 112300358 A CN112300358 A CN 112300358A
Authority
CN
China
Prior art keywords
reaction
quaternary ammonium
glycidyl ether
ammonium salt
solvent
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
CN202010460317.9A
Other languages
Chinese (zh)
Inventor
王贵富
张弢
杜鹏
余立挺
张绳延
曾嘉华
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.)
Nanjing Shanwei New Material Technology Co ltd
Original Assignee
Nanjing Shanwei New Material Technology Co ltd
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 Nanjing Shanwei New Material Technology Co ltd filed Critical Nanjing Shanwei New Material Technology Co ltd
Priority to CN202010460317.9A priority Critical patent/CN112300358A/en
Publication of CN112300358A publication Critical patent/CN112300358A/en
Pending legal-status Critical Current

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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3278—Hydroxyamines containing at least three hydroxy groups
    • C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides a solvent-free ultraviolet curing quaternary ammonium salt resin and a preparation method thereof. Which comprises the following steps: the hydroxyalkylamine is subjected to ring-opening reaction with alkyl glycidyl ether, then is subjected to reaction with polyisocyanate and hydroxy acrylate, and finally is subjected to reaction with halogenated alkane to obtain the solvent-free ultraviolet curing quaternary ammonium salt resin. The method has the advantages of cheap and easily-obtained raw materials, mild reaction conditions, no solvent participation in the reaction process and simple operation. The quaternary ammonium salt resin has the characteristics of good antifogging performance and rapid photocuring.

Description

Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to solvent-free ultraviolet curing quaternary ammonium salt resin and a preparation method thereof.
Background
When water vapor is condensed into liquid drops on the surface of the transparent solid material, the scattering performance of light on the surface of the material is increased, so that the light directly penetrating through the surface of the solid material is weakened, and the use of the transparent solid material is further influenced. For example, at low temperature, the atomization phenomenon occurs on transparent materials such as windows, glasses, various protective glasses, windshields and solar panels, which are closely related to our lives, which affects people's lives and is more likely to endanger people's safety. Therefore, the research on the anti-fog method and the anti-fog material is very important.
Currently, antifogging methods are mainly heating, convection and paint methods. Although the former two methods can effectively prevent the water vapor from being atomized, the methods have the disadvantages of high energy consumption, high operation cost and certain limitations. The coating method solves the defects of the former two methods to a certain extent and has good antifogging property. The antifogging coatings used by the coating method mainly comprise four types, namely water-based antifogging coatings, ultraviolet curing antifogging coatings, organic-inorganic hybrid antifogging coatings and nano antifogging coatings. Among them, the ultraviolet curing coating is a novel green environment-friendly coating, has the advantages of high curing rate, less environmental pollution, low energy consumption, high coating film quality and the like, and is one of the main directions for developing antifogging coatings.
The quaternary ammonium salt is a common cationic surfactant, and the hydrophilic group of the quaternary ammonium salt has positive charge, so that the quaternary ammonium salt has a unique steric effect. The quaternary ammonium salt cationic surfactant has good bactericidal performance, biodegradability and excellent adsorbability, and the coating compounded by the quaternary ammonium salt cationic surfactant has good antifogging performance. Although quaternary ammonium cationic surfactants have been studied more, photocured quaternary ammonium salts have been studied less.
Disclosure of Invention
The invention aims to provide a solvent-free ultraviolet curing quaternary ammonium salt resin, which is characterized in that quaternary ammonium salt is introduced into urethane acrylate resin to obtain the solvent-free ultraviolet curing quaternary ammonium salt resin with good antifogging performance and rapid photocuring.
The invention aims to provide a preparation method of solvent-free ultraviolet curing quaternary ammonium salt resin, which has the advantages of cheap and easily obtained raw materials, mild reaction conditions, no solvent participation in the reaction process and simple operation.
A preparation method of solvent-free ultraviolet curing quaternary ammonium salt resin comprises the following steps:
(1) adding hydroxyalkylamine into a dry reaction bottle at room temperature, and heating to 55-65 ℃;
(2) adding alkyl glycidyl ether into a reaction bottle in batches, heating to 65-75 ℃, stirring for reaction for 2 hours, and cooling the reaction solution to room temperature;
(3) adding hydroxyl acrylate and a polymerization inhibitor into a reaction bottle at room temperature, dropwise adding a mixed solution of polyisocyanate and a catalyst into the reaction bottle, heating to 60-70 ℃, and stirring for reaction until the measured-NCO value reaches a theoretical value;
(4) and cooling to 40-50 ℃, then dropwise adding the halogenated alkane into a reaction bottle, keeping the temperature and continuously reacting to finally obtain the solvent-free ultraviolet curing quaternary ammonium salt resin.
The determination method of the-NCO content is a di-n-butylamine back titration method.
The catalyst is dibutyltin dilaurate, stannous octoate, N-dimethylethanolamine and the like.
The polymerization inhibitor is 2, 6-p-di-tert-butyl-p-cresol, p-methoxyphenol and the like.
The polyisocyanate is isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate biuret, or the mixture thereof.
The hydroxyl acrylate is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polycaprolactone acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, etc., or a mixture thereof.
The alkyl glycidyl ether is dodecyl glycidyl ether, octadecyl glycidyl ether, dodecyl-tetradecyl glycidyl ether, etc., or their mixture.
The hydroxy alkylamine is ethanolamine, propanolamine, butanolamine, hexanolamine, octanolamine, etc., or the mixture of the ethanolamine, the propanolamine, the butanolamine, the hexanolamine, the octanolamine, etc.
The halogenated alkane is methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, chlorooctane, octyl bromide, octyl iodide and the like, or the mixture of the methyl bromide, the methyl iodide, the ethyl chloride, the ethyl bromide, the ethyl iodide, the chlorooctane, the octyl bromide, the octyl iodide and the like.
The mass ratio of the hydroxy alkylamine to the alkyl glycidyl ether is 1: 2.
The mass ratio of the polyisocyanate to the hydroxyalkylamine is 1:1 or 1: 2.
The mass ratio of the polyisocyanate to the hydroxy acrylate is 1:1 or 1: 2.
The mass ratio of the hydroxy alkyl amine to the halogenated alkane is 1: 1.
According to the invention, the amino group of the hydroxy alkylamine reacts with the epoxy group of the alkyl glycidyl ether to successfully obtain the hydroxy alkyl tertiary amine, and the hydroxy tertiary amine can continuously react with the halogenated alkane to obtain the quaternary ammonium salt with a special space effect.
According to the invention, unsaturated carbon-carbon double bonds are introduced into the resin through the reaction of isocyanate groups of polyisocyanate and terminal hydroxyl groups, so that the photocuring efficiency of the resin is improved; on the other hand, quaternary ammonium salt with unique space effect is introduced into the resin, so that the resin has good antifogging performance.
The invention provides a preparation method of solvent-free ultraviolet curing quaternary ammonium salt resin, which has the advantages of simple and easily obtained raw materials, mild reaction conditions and simple operation.
Drawings
FIG. 1 is a synthetic route of solvent-free UV-curable quaternary ammonium salt resin.
Detailed Description
The preparation method of the solvent-free uv curable quaternary ammonium salt resin according to the present invention will be further described with reference to the following specific examples, but the present invention is not limited to the examples.
Example 1:
(1) adding 1.0mol of ethanolamine into a dry reaction bottle at room temperature, and heating to 58 ℃;
(2) adding 2.0mol of dodecyl glycidyl ether into a reaction bottle in batches, heating to 70 ℃, stirring for reaction for 2 hours, and then cooling the reaction solution to room temperature;
(3) at room temperature, adding 1.0mol of pentaerythritol triacrylate and 0.2 wt% of 2, 6-p-di-tert-butyl-p-cresol into a reaction bottle, dropwise adding a mixed solution of 1.0mol of isophorone diisocyanate and a proper amount of dibutyltin dilaurate into the reaction bottle, heating to 60 ℃, and stirring for reaction until the measured-NCO value is 0.18%;
(4) and (3) cooling to 40 ℃, then dropwise adding 1.0mol of bromoethane into the reaction bottle, keeping the temperature, and continuing to react for 1 hour to finally obtain the solvent-free ultraviolet curing quaternary ammonium salt resin.
Example 2:
(1) adding 1.0mol of ethanolamine into a dry reaction bottle at room temperature, and heating to 60 ℃;
(2) adding 2.0mol of tetradecyl glycidyl ether into a reaction bottle in batches, heating to 70 ℃, stirring for reacting for 2 hours, and cooling the reaction solution to room temperature;
(3) at room temperature, adding 1.0mol of pentaerythritol triacrylate and 0.2 wt% of 2, 6-p-di-tert-butyl-p-cresol into a reaction bottle, dropwise adding a mixed solution of 1.0mol of hexamethylene diisocyanate and a proper amount of dibutyltin dilaurate into the reaction bottle, heating to 65 ℃, and stirring for reaction until the measured-NCO value is 0.20%;
(4) and (3) cooling to 42 ℃, then dropwise adding 1.0mol of bromoethane into the reaction bottle, keeping the temperature, and continuing to react for 1 hour to finally obtain the solvent-free ultraviolet curing quaternary ammonium salt resin.
Example 3:
(1) adding 0.5mol of ethanolamine into a dry reaction bottle at room temperature, and heating to 60 ℃;
(2) adding 1.0mol of dodecyl-tetradecyl glycidyl ether into a reaction bottle in batches, heating to 70 ℃, stirring for reacting for 2 hours, and cooling the reaction solution to room temperature;
(3) at room temperature, adding 0.5mol of pentaerythritol triacrylate and 0.2 wt% of 2, 6-p-di-tert-butyl-p-cresol into a reaction bottle, dropwise adding a mixed solution of 1.0mol of hexamethylene diisocyanate and a proper amount of dibutyltin dilaurate into the reaction bottle, heating to 65 ℃, and stirring for reaction until the measured-NCO value is 0.15%;
(4) and (3) cooling to 40 ℃, then dropwise adding 0.5mol of bromoethane into the reaction bottle, keeping the temperature, and continuing to react for 1 hour to finally obtain the solvent-free ultraviolet curing quaternary ammonium salt resin.
Example 4:
(1) adding 0.5mol of ethanolamine into a dry reaction bottle at room temperature, and heating to 60 ℃;
(2) adding 1.0mol of dodecyl-tetradecyl glycidyl ether into a reaction bottle in batches, heating to 70 ℃, stirring for reacting for 2 hours, and cooling the reaction solution to room temperature;
(3) at room temperature, adding 0.5mol of pentaerythritol triacrylate and 0.2 wt% of 2, 6-p-di-tert-butyl-p-cresol into a reaction bottle, dropwise adding a mixed solution of 1.0mol of isophorone diisocyanate and a proper amount of dibutyltin dilaurate into the reaction bottle, heating to 65 ℃, and stirring for reaction until the measured-NCO value is 0.18%;
(4) and (3) cooling to 40 ℃, then dropwise adding 0.5mol of octyl bromide into the reaction bottle, keeping the temperature, and continuing to react for 1 hour to finally obtain the solvent-free ultraviolet curing quaternary ammonium salt resin.

Claims (13)

1. A preparation method of solvent-free ultraviolet curing quaternary ammonium salt resin comprises the following steps:
(1) adding hydroxyalkylamine into a dry reaction bottle at room temperature, and heating to 55-65 ℃;
(2) adding alkyl glycidyl ether into a reaction bottle in batches, heating to 65-75 ℃, stirring for reaction for 2 hours, and cooling the reaction solution to room temperature;
(3) adding hydroxyl acrylate and a polymerization inhibitor into a reaction bottle at room temperature, dropwise adding a mixed solution of polyisocyanate and a catalyst into the reaction bottle, heating to 60-70 ℃, and stirring for reaction until the measured-NCO value reaches a theoretical value;
(4) and cooling to 40-50 ℃, then dropwise adding the halogenated alkane into a reaction bottle, keeping the temperature and continuously reacting to finally obtain the solvent-free ultraviolet curing quaternary ammonium salt resin.
2. The method for determining the-NCO content according to claim 1, which is a di-n-butylamine back titration method.
3. The catalyst of claim 1 is dibutyltin dilaurate, stannous octoate, N-dimethylethanolamine, or the like.
4. The polymerization inhibitor according to claim 1, which is 2, 6-p-di-t-butyl-p-cresol, p-methoxyphenol or the like.
5. The polyisocyanate according to claim 1 is isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate biuret, or the like, or a mixture thereof, or the like.
6. The hydroxyacrylate of claim 1 is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polycaprolactone acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, and the like, or mixtures thereof.
7. The alkyl glycidyl ether of claim 1 is dodecyl glycidyl ether, octadecyl glycidyl ether, octa-decyl glycidyl ether, dodecyl-tetradecyl glycidyl ether, etc., or a mixture thereof.
8. The hydroxyalkylamine of claim 1 is ethanolamine, propanolamine, butanolamine, hexanolamine, octanolamine, and the like, or mixtures thereof.
9. The halogenated alkane according to claim 1, which is methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, chlorooctane, octyl bromide, octyl iodide, etc., or a mixture thereof.
10. The mass ratio of hydroxyalkylamine to alkyl glycidyl ether of claim 1 or 7 to 8 is 1: 2.
11. The mass ratio of polyisocyanate to hydroxyalkylamine as in claim 1 or 5 or 8 is 1:1 or 1: 2.
12. The mass ratio of polyisocyanate to hydroxyacrylate according to claims 1 or 5 to 6 is 1:1 or 1: 2.
13. The mass ratio of hydroxyalkylamine to haloalkane of claims 1 or 8-9 is 1: 1.
CN202010460317.9A 2020-05-27 2020-05-27 Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof Pending CN112300358A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010460317.9A CN112300358A (en) 2020-05-27 2020-05-27 Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010460317.9A CN112300358A (en) 2020-05-27 2020-05-27 Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112300358A true CN112300358A (en) 2021-02-02

Family

ID=74336576

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010460317.9A Pending CN112300358A (en) 2020-05-27 2020-05-27 Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112300358A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113024868A (en) * 2021-03-04 2021-06-25 浙江伟星光学有限公司 Antibacterial resin lens and preparation method thereof

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1145926A (en) * 1995-03-27 1997-03-26 大日本油墨化学工业株式会社 Energy ray curable resin composition and method for producing the same
KR20030078233A (en) * 2002-03-28 2003-10-08 학교법인조선대학교 UV curable quaternary ammonium salt with excellent scratch resistance and curing behavior, process for preparing thereof, and UV curable resin composition
CN1814674A (en) * 2005-02-04 2006-08-09 日本合成化学工业株式会社 Activity energy-line solidifying type resin composition
CN1968979A (en) * 2004-04-29 2007-05-23 亚什兰许可和知识产权有限公司 Self-photoinitiating water-dispersible acrylate ionomers and synthetic methods
CN101581039A (en) * 2009-06-12 2009-11-18 辽宁恒星精细化工（集团）有限公司 Durable antistatic finishing agent for fabrics and preparation method
CN103333314A (en) * 2013-06-09 2013-10-02 广东工业大学 Cation photocuring fluorinated polyurethane resin and preparation method thereof
CN103422352A (en) * 2013-07-31 2013-12-04 天津新纶科技有限公司 Polyhydroxyl polyether chain segment quaternary ammonium salt antistatic agent and preparation method thereof, and antistatic finishing agent prepared by same
CN103554352A (en) * 2013-09-29 2014-02-05 中国海洋石油总公司 Pigment dispersion resin used for acrylic series cathode electrophoretic coating and pigment slurry thereof
CN105176155A (en) * 2015-07-29 2015-12-23 华南理工大学 UV cured cathode electrophoresis paint with side chain containing ammonium salt positive ions and preparation method therefor
CN106459240A (en) * 2014-06-27 2017-02-22 Dic株式会社 Active energy ray-curable composition and film using same
CN108456290A (en) * 2017-12-28 2018-08-28 滁州金桥德克新材料有限公司 A kind of dual cure polyurethane acrylate resin and preparation method thereof
CN110643037A (en) * 2019-09-26 2020-01-03 南京林业大学 Preparation method of polymer solution containing quaternary ammonium salt, tertiary ammonium salt and tertiary amine on main chain
CN110724247A (en) * 2019-10-11 2020-01-24 江苏富琪森新材料有限公司 A kind of preparation method of cationic photocurable water-based polyurethane emulsifier

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1145926A (en) * 1995-03-27 1997-03-26 大日本油墨化学工业株式会社 Energy ray curable resin composition and method for producing the same
KR20030078233A (en) * 2002-03-28 2003-10-08 학교법인조선대학교 UV curable quaternary ammonium salt with excellent scratch resistance and curing behavior, process for preparing thereof, and UV curable resin composition
CN1968979A (en) * 2004-04-29 2007-05-23 亚什兰许可和知识产权有限公司 Self-photoinitiating water-dispersible acrylate ionomers and synthetic methods
CN1814674A (en) * 2005-02-04 2006-08-09 日本合成化学工业株式会社 Activity energy-line solidifying type resin composition
CN101581039A (en) * 2009-06-12 2009-11-18 辽宁恒星精细化工（集团）有限公司 Durable antistatic finishing agent for fabrics and preparation method
CN103333314A (en) * 2013-06-09 2013-10-02 广东工业大学 Cation photocuring fluorinated polyurethane resin and preparation method thereof
CN103422352A (en) * 2013-07-31 2013-12-04 天津新纶科技有限公司 Polyhydroxyl polyether chain segment quaternary ammonium salt antistatic agent and preparation method thereof, and antistatic finishing agent prepared by same
CN103554352A (en) * 2013-09-29 2014-02-05 中国海洋石油总公司 Pigment dispersion resin used for acrylic series cathode electrophoretic coating and pigment slurry thereof
CN106459240A (en) * 2014-06-27 2017-02-22 Dic株式会社 Active energy ray-curable composition and film using same
CN105176155A (en) * 2015-07-29 2015-12-23 华南理工大学 UV cured cathode electrophoresis paint with side chain containing ammonium salt positive ions and preparation method therefor
CN108456290A (en) * 2017-12-28 2018-08-28 滁州金桥德克新材料有限公司 A kind of dual cure polyurethane acrylate resin and preparation method thereof
CN110643037A (en) * 2019-09-26 2020-01-03 南京林业大学 Preparation method of polymer solution containing quaternary ammonium salt, tertiary ammonium salt and tertiary amine on main chain
CN110724247A (en) * 2019-10-11 2020-01-24 江苏富琪森新材料有限公司 A kind of preparation method of cationic photocurable water-based polyurethane emulsifier

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113024868A (en) * 2021-03-04 2021-06-25 浙江伟星光学有限公司 Antibacterial resin lens and preparation method thereof

Similar Documents

Publication Publication Date Title
US5696291A (en) Cationic polyurethane compositions, quaternary ammonium salts and methods for their preparation
US4327008A (en) Urethane rheology modifiers and coating compositions containing same
US6207744B1 (en) Curable polyurethane polymer dispersion based on this polymer, processing for preparing the dispersion, and its use
CN106750140B (en) Amine modified urethane acrylate photocuring resin and preparation method thereof
US6069217A (en) Urethane-acrylic copolymer thickening compositions for aqueous systems
CN109651922B (en) A kind of water-based polyurethane toughening water-based epoxy resin anti-corrosion coating and preparation method
CN109761834A (en) A kind of preparation method and application of the dispersible polyaspartic ester resin of water and aqueous carbamide paint
CN101418145B (en) Cation waterborne ultraviolet curing resin coating and production method
US4761465A (en) Difunctional isocyanate-terminated polyoxyalkylene diamine prepolymers and polymer coatings applications
EP2287260A1 (en) Networkable polyurethane dispersions
JPH01168756A (en) Aqueous polymer dispersion, coating or film derived therefrom and composite material
TW200408678A (en) Radiation-curable polyurethane dispersion
CN1446239A (en) Aqueous cross-linkable binder composition and its use in production of lacquer coatings
JPH08501329A (en) Polyurethane, its use and water-based paint containing polyurethane as a thickener
US5200463A (en) Aqueous, radiation-curable urethane acrylate emulsions and process for producing the same
CN103333314A (en) Cation photocuring fluorinated polyurethane resin and preparation method thereof
CN102276502B (en) Method for preparing ultraviolet cured polyurethane acrylate oligomer
CN108239457B (en) Water-based peelable glue, and preparation method and application thereof
CN112300358A (en) Solvent-free ultraviolet curing quaternary ammonium salt resin and preparation method thereof
JP4222647B2 (en) Novel dispersants for aqueous coating compositions
US4337184A (en) Urethane rheology modifiers substantially free of terminal hydrophobic groups and compositions containing same
JP4989813B2 (en) Urethane (meth) acrylate oligomer and antistatic coating composition containing the same
CN114149565A (en) Preparation method of light-curable hyperbranched polyurethane-epoxy acrylate
CN105038487B (en) Aqueous anticorrosive coating peculiar to vessel of one kind and preparation method thereof
US4373083A (en) Process of making urethane rheology modifiers

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20210202