CN103642383B

CN103642383B - A kind of preparation method of eigenmode photocuring antistatic resin

Info

Publication number: CN103642383B
Application number: CN201310646019.9A
Authority: CN
Inventors: 姚伯龙; 韩兵; 齐会民; 倪才华; 王利魁; 李根龙; 张国标; 齐家鹏
Original assignee: Jiangnan University
Current assignee: Jiangnan University
Priority date: 2013-12-04
Filing date: 2013-12-04
Publication date: 2016-04-20
Anticipated expiration: 2033-12-04
Also published as: CN103642383A

Abstract

A kind of preparation method of eigenmode photocuring antistatic resin, it is with PTMG (PTMG1000), polycarbonate diol (PCDL1000), isophorone diisocyanate (IPDI), 1, ammediol, 2,4-diamino benzene sulfonic acid sodium (DASS) and Hydroxyethyl acrylate (HEA) are raw material, have synthesized a kind of ultraviolet light polymerization sulfonate type polyurethane acrylate prepolymer; This prepolymer reacts with 3,4-rthylene dioxythiophene (EDOT) after emulsification, namely obtains a kind of eigenmode photocuring antistatic resin.This resin can fast setting film forming through ultraviolet lighting under the catalysis of light trigger, and the mechanical property after film forming is superior, and static resistance is good; The fields such as indicating meter, Communication Equipment, electrical equipment, electronic product can be widely used in the antistatic coating of this resin prepared by film forming matrix resin.

Description

A kind of preparation method of eigenmode photocuring antistatic resin

Technical field

A preparation method for eigenmode photocuring antistatic resin, belongs to ultraviolet-curing paint field.

Background technology

Antistatic resin is the functional resin having conduction and get rid of accumulate static charge ability.Antistatic resin may be used on antistatic coating field, solves the relevant difficult problems such as statics.

Antistatic coating comprises doping type and eigenmode two kinds on the whole, and traditional antistatic coating mostly is doping type.The mechanism of doping type antistatic coating is a certain amount of conductive filler material that adulterates in nonconducting matrix resin, makes it have anlistatig function; Antistatic coating prepared by this method, for reaching good static resistance, must make the volume fraction of conductive filler material reach certain degree and could form conductive network or conductive path, and therefore its shortcoming is that the density of electrically conducting coating is large, conducts electricity uneven.The present invention adopts UV-curing technology to synthesize a kind of eigenmode antistatic resin, namely has static resistance when not adding conductive filler material, can solve the difficult problem that coating density is large and conduction is uneven.This process for preparing resins is more convenient, and cost is lower, can be widely used in the fields such as indicating meter, Communication Equipment, electrical equipment, electronic product.

Summary of the invention

The object of the invention is to design the photocuring eigenmode antistatic resin having better performance at everyways such as thermostability, sticking power, weathering resistance, wear resistance, static resistances, after it makes antistatic coating, the fields such as indicating meter, Communication Equipment, electrical equipment, electronic product can be widely used in.

Technical scheme of the present invention: a kind of preparation method of eigenmode photocuring antistatic resin, concrete steps are:

(1) preparation of photocuring sulfonate type urethane acrylate: add a certain amount of isophorone diisocyanate (IPDI) in the dry there-necked flask that agitator is housed, then add the positive fourth tin (DBTDL) of several catalyst dibutyltin cinnamic acids two; Take the mixture of a certain amount of PTMG PTMG1000 and polycarbonate diol PCDL1000, add in dropping funnel, shake up, drip, it is 55 DEG C, after dropwising that temperature controls, and continues reaction 1.5h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, adding a certain amount of 1,3-PD, being warming up to 75 DEG C, continue reaction 1h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, adding a certain amount of 2,4-diamino benzene sulfonic acid sodium (DASS), continuing reaction 2.5h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value,

Add a certain amount of Hydroxyethyl acrylate (HEA) and continue reaction, whole reaction process is all with acetone hierarchy of control viscosity; When NCO reaches theoretical value, reaction terminates, and products therefrom is designated as A.

(2) preparation of photocuring eigenmode antistatic resin: add a certain amount of product A in the dry there-necked flask that agitator is housed, the deionized water of metering is added in dropping funnel, in the speed instillation there-necked flask dripped with 2 ~ 3s/, rapid stirring reaction 6h, obtain a kind of emulsion and take a certain amount of 3, 4-ethene dioxythiophene (EDOT) adds this in emulsion, mol ratio is 1: 1.5-1.8, add a certain amount of oxygenant iron(ic) chloride again, catalyst sulfuric acid iron, rapid stirring reaction 12h under room temperature, obtain mazarine water dispersion, dewater drying, products therefrom is designated as B.

(3) preparation of photocuring antistatic film: add a certain amount of product B in the there-necked flask being added with proper amount of acetone, adds appropriate light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone wherein, and continue reaction 1h, products therefrom is designated as C; C is applied on the tinplate sheet of polishing, after solvent evaporates, can fast setting film forming under ultraviolet lighting.

Embodiment

Embodiment 1:

In the dry there-necked flask that agitator is housed, add 14.2g isophorone diisocyanate (IPDI), then add the positive fourth tin (DBTDL) of 0.03g tin dilaurate two; Take 15.2g PTMG PTMG1000 and 16.3g polycarbonate diol PCDL1000 respectively, add in dropping funnel, shake up, drip, it is 55 DEG C, after dropwising that temperature controls, and continues reaction 1.5h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, adding 3.53g1, ammediol, being warming up to 75 DEG C, continue reaction 1h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, adding 0.75g2,4-diamino benzene sulfonic acid sodium (DASS), continuing reaction 2.5h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, add 4.26g Hydroxyethyl acrylate (HEA) and continue reaction, whole reaction process is all with acetone hierarchy of control viscosity; When NCO reaches theoretical value, reaction terminates, and products therefrom is designated as A.

In the dry there-necked flask that agitator is housed, add 15g product A, add 14.5g deionized water in dropping funnel, in the speed instillation there-necked flask dripped with 2-3s/, rapid stirring reaction 6h, obtains a kind of emulsion; Take 1.62g3,4-ethene dioxythiophene (EDOT) joins in this emulsion, then adds 1.92g iron(ic) chloride, 0.017g ferric sulfate, and rapid stirring reaction 12h under room temperature, obtain mazarine water dispersion, dewater drying, and products therefrom is designated as B.

In the there-necked flask being added with proper amount of acetone, add 10g product B, add 0.26g light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone wherein, continue reaction 1h, products therefrom is designated as C; C is applied on the tinplate sheet of polishing, after solvent evaporates, can fast setting film forming under ultraviolet lighting.

Embodiment 2:

In the dry there-necked flask that agitator is housed, add 25.6g isophorone diisocyanate (IPDI), then add the positive fourth tin (DBTDL) of 0.04g tin dilaurate two; Take 24.7g PTMG PTMG1000 and 19.8g polycarbonate diol PCDL1000 respectively, add in dropping funnel, shake up, drip, it is 55 DEG C, after dropwising that temperature controls, and continues reaction 1.5h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, adding 6.28g1, ammediol, being warming up to 75 DEG C, continue reaction 1h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, adding 1.69g2,4-diamino benzene sulfonic acid sodium (DASS), continuing reaction 2.5h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, add 7.91g Hydroxyethyl acrylate (HEA) and continue reaction, whole reaction process is all with acetone hierarchy of control viscosity; When NCO reaches theoretical value, reaction terminates, and products therefrom is designated as A.

In the dry there-necked flask that agitator is housed, add 23g product A, add 27.5g deionized water in dropping funnel, in the speed instillation there-necked flask dripped with 2-3s/, rapid stirring reaction 6h, obtains a kind of emulsion; Take 2.33g3,4-ethene dioxythiophene (EDOT) joins in this emulsion, then adds 2.56g iron(ic) chloride, 0.023g ferric sulfate, and rapid stirring reaction 12h under room temperature, obtain mazarine water dispersion, dewater drying, and products therefrom is designated as B.

In the there-necked flask being added with proper amount of acetone, add 20g product B, add 0.46g light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone wherein, continue reaction 1h, products therefrom is designated as C; C is applied on the tinplate sheet of polishing, after solvent evaporates, can fast setting film forming under ultraviolet lighting.

Claims

1. a preparation method for eigenmode photocuring antistatic resin, is characterized in that, comprises the steps:

(1) preparation of photocuring sulfonate type urethane acrylate: add a certain amount of isophorone diisocyanate (IPDI) in the dry there-necked flask that agitator is housed, then add the positive fourth tin (DBTDL) of several catalyst dibutyltin cinnamic acids two; Take the mixture of a certain amount of PTMG PTMG1000 and polycarbonate diol PCDL1000, add in dropping funnel, shake up, drip, it is 55 DEG C, after dropwising that temperature controls, and continues reaction 1.5h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, adding a certain amount of 1,3-PD, being warming up to 75 DEG C, continue reaction 1h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, adding a certain amount of 2,4-diamino benzene sulfonic acid sodium (DASS), continuing reaction 2.5h; With the change of nco value in Di-n-Butyl Amine method monitoring system, when reaching theoretical value, add a certain amount of Hydroxyethyl acrylate (HEA) and continue reaction, whole reaction process is all with acetone hierarchy of control viscosity; When NCO reaches theoretical value, reaction terminates, and products therefrom is designated as A;

(2) preparation of photocuring eigenmode antistatic resin: add a certain amount of product A in the dry there-necked flask that agitator is housed, the deionized water of metering is added in dropping funnel, in the speed instillation there-necked flask dripped with 2 ~ 3s/, rapid stirring reaction 6h, obtains a kind of emulsion; Take a certain amount of 3,4-ethene dioxythiophene (EDOT) joins in this emulsion, mol ratio is 1: 1.5 ~ 1.8, add a certain amount of oxygenant iron(ic) chloride, catalyst sulfuric acid iron again, rapid stirring reaction 12h under room temperature, obtain mazarine water dispersion, dewater drying, and products therefrom is designated as B;