CN111269378B

CN111269378B - High-elasticity water-based UV resin and preparation method thereof

Info

Publication number: CN111269378B
Application number: CN202010180229.3A
Authority: CN
Inventors: 李毅全; 夏同祥
Original assignee: Jiangmen Hengzhiguang Environmental Protection New Material Co ltd
Current assignee: Guangdong Hengzhiguang Environmental Protection New Materials Co ltd
Priority date: 2020-03-16
Filing date: 2020-03-16
Publication date: 2021-11-30
Anticipated expiration: 2040-03-16
Also published as: CN111269378A

Abstract

The invention relates to the technical field of UV (ultraviolet) resin, in particular to high-elasticity water-based UV resin and a preparation method thereof. The coating at least comprises the following components in parts by weight: 35-45 parts of isocyanate, 0.05-0.2 part of catalyst, 0.1-0.3 part of polymerization inhibitor, 25-35 parts of organic silicon compound, 25-35 parts of polyol, 3-12 parts of nano particles, 5-15 parts of hydroxyl acrylate and 5-10 parts of neutralizer. The invention adopts isocyanate, catalyst, polyalcohol, nano particles, organosilicon compound and the like to prepare the water-based UV resin, the components have good synergistic effect, the prepared water-based UV resin has high curing rate, high hardness, good glossiness, high elasticity and high wear resistance, and can be widely applied to the surfaces of membrane materials such as PMMA, PC, PET, composite plates and the like and materials such as hardware, stainless steel and the like.

Description

High-elasticity water-based UV resin and preparation method thereof

Technical Field

The invention relates to the technical field of UV (ultraviolet) resin, in particular to high-elasticity water-based UV resin and a preparation method thereof.

Background

Ultraviolet (UV) curing technology is a new curing technology developed in the 60 s of the 20 th century, and is a great concern in the paint industry because it meets the requirements of the development of modern green and environment-friendly environments. The uv curing process is actually a chemical reaction process, generally using uv light as a curing energy source to rapidly crosslink and cure small molecule liquid functionality monomers or large molecule functionality oligomers into a large molecule network in a very short time. The ultraviolet curing technology has wide application range and mainly relates to the fields of coating, printing ink, adhesive, photoresist (photoresist), three-dimensional laser forming and the like.

The UV resin, also called photosensitive resin, liquid light-cured resin and liquid photosensitive resin, is a material for light-cured rapid prototyping and mainly comprises an oligomer, a photoinitiator and a diluent. The polyurethane acrylate waterborne UV resin (UV-WPUA) is the most researched ultraviolet curing waterborne system at present, has wide application, and can be widely applied to various fields such as wood, automobiles, biological materials, electronic materials, leather and the like. Generally, the preparation of the urethane acrylate waterborne UV resin adopts an acrylic compound containing double bonds and hydroxyl groups, and introduces carbon-carbon double bonds (C ═ C) into the main chain of polyurethane by utilizing the reaction of the hydroxyl groups and isocyanate groups so as to endow the polyurethane with photocuring performance. Although many studies have been made on urethane acrylate aqueous UV resins in recent years, the urethane acrylate aqueous UV resins still have problems such as susceptibility to abrasion.

In view of the above problems, the present invention is directed to provide a high-elasticity aqueous UV resin which has high elasticity and wear resistance and can be widely applied to film materials such as PMMA, PC, PET, composite plates, and the like, and surfaces of materials such as hardware, stainless steel, and the like.

Disclosure of Invention

In order to solve the above problems, a first aspect of the present invention provides a highly elastic aqueous UV resin comprising at least the following components in parts by weight: 35-45 parts of isocyanate, 0.05-0.2 part of catalyst, 0.1-0.3 part of polymerization inhibitor, 25-35 parts of organic silicon compound, 25-35 parts of polyol, 3-12 parts of nano particles, 5-15 parts of hydroxyl acrylate and 5-10 parts of neutralizer.

As a preferable technical scheme, the catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate and triethylenediamine.

As a preferable technical scheme, the polymerization inhibitor is selected from at least one of di-tert-amyl hydroquinone, dinitro-p-cresol, dinitro-sec-butylphenol, p-tert-butyl catechol, di-tert-butyl-p-ethylphenol, 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical, p-methoxyphenol, p-hydroxy phenetole and hydroquinone.

As a preferable technical solution, the organic silicon compound is at least one selected from hydroxyl silicone oil, amino silicone oil and alkyl hydroxyl silicone oil.

In a preferred embodiment, the polyol is at least one selected from polytetrahydrofuran ether glycol, polybutylene adipate glycol, polycarbonate diol, polyethylene glycol, ethylene glycol, and butanediol.

As a preferable technical scheme, raw materials for preparing the nano particles comprise graphene oxide, silicon dioxide and 4-aminobutyltriethoxysilane.

As a preferable technical scheme, in the raw materials for preparing the nano particles, the average particle diameters of graphene oxide and silicon dioxide are respectively 20-30 nm.

As a preferred technical scheme, in the raw materials for preparing the nanoparticles, the weight ratio of graphene oxide to silicon dioxide is (0.06-0.1): 1.

as a preferable technical solution, the hydroxyl acrylate is at least one selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

The second aspect of the invention provides a preparation method of a high-elasticity water-based UV resin, which at least comprises the following steps: mixing isocyanate, a catalyst, polyol, nano particles and an organic silicon compound, reacting for 2-3h at 40-60 ℃, adding a polymerization inhibitor and hydroxy acrylate, reacting for 2-3h at 60-80 ℃, adding a neutralizer and water at 40-45 ℃, adjusting the pH value to 7, and stirring for reacting for 1-3h to obtain the high-elasticity waterborne UV resin.

Has the advantages that: the invention adopts isocyanate, catalyst, polyalcohol, nano particles, organosilicon compound, polymerization inhibitor, hydroxy acrylate and neutralizer to prepare the waterborne UV resin together, the components have better synergistic effect, the prepared waterborne UV resin has fast curing speed, high hardness, good glossiness, higher elasticity and wear resistance, and can be widely applied to the surfaces of membrane materials such as PMMA, PC, PET, composite plates and the like and materials such as hardware, stainless steel and the like.

Detailed Description

The technical features in the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, but the scope of protection of the present invention is not limited thereto.

"preferred", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

The invention provides a high-elasticity water-based UV resin, which at least comprises the following components in parts by weight: 35-45 parts of isocyanate, 0.05-0.2 part of catalyst, 0.1-0.3 part of polymerization inhibitor, 25-35 parts of organic silicon compound, 25-35 parts of polyol, 3-12 parts of nano particles, 5-15 parts of hydroxyl acrylate and 5-10 parts of neutralizer.

In a preferred embodiment, at least the following ingredients are included in parts by weight: 40 parts of isocyanate, 0.1 part of catalyst, 0.2 part of polymerization inhibitor, 30 parts of organic silicon compound, 30 parts of polyalcohol, 8 parts of nano particles, 10 parts of hydroxy acrylate and 8 parts of neutralizer.

Isocyanates

Isocyanates are a generic term for the various esters of isocyanic acid. When classified by the number of-NCO groups, the polyisocyanates include monoisocyanates R-N ═ C ═ O and diisocyanates O ═ C ═ N-R-N ═ C ═ O, polyisocyanates, and the like.

In a preferred embodiment, the isocyanate is selected from at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate.

In a more preferred embodiment, the isocyanate is diphenylmethane diisocyanate.

The diphenylmethane diisocyanate described herein is not particularly limited and may be prepared, for example, by reacting a free amine with phosgene; diphenylmethane diisocyanates are also commercially available, such as are commercially available including, but not limited to, from Douglas chemical products, Inc.

Catalyst and process for preparing same

A substance that can change (increase or decrease) the chemical reaction rate of a reactant in a chemical reaction without changing the chemical equilibrium and whose own mass and chemical properties are not changed before and after the chemical reaction is called a catalyst (solid catalyst is also called a catalyst).

In a preferred embodiment, the catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, and triethylenediamine.

In a more preferred embodiment, the catalyst is stannous octoate.

The CAS number of the stannous octoate is 301-10-0.

Polymerization inhibitor

The polymerization inhibitor is an industrial aid, and is generally used to prevent the progress of polymerization. The inhibitor molecules react with the chain radicals to form non-radical species or low reactive radicals that cannot initiate, thereby terminating the polymerization.

In a preferred embodiment, the polymerization inhibitor is selected from at least one of di-tert-amyl hydroquinone, dinitro-p-cresol, dinitro-sec-butylphenol, p-tert-butyl catechol, di-tert-butyl-p-ethylphenol, 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl, p-methoxyphenol, p-hydroxy phenetole and hydroquinone.

In a more preferred embodiment, the polymerization inhibitor is di-tert-butyl-p-ethylphenol.

In a more preferred embodiment, the polymerization inhibitor is 2, 6-di-tert-butyl-p-ethylphenol.

The CAS number of the 2, 6-di-tert-butyl-p-ethylphenol is 4130-42-1.

Organosilicon compounds

Organosilicon compounds, i.e., organosilicon compounds, are those which contain Si-C bonds and at least one organic radical which is bonded directly to the silicon atom, and compounds in which an organic radical is bonded to a silicon atom via oxygen, sulfur, nitrogen, or the like are also conventionally used as organosilicon compounds.

In a preferred embodiment, the organosilicon compound is at least one selected from the group consisting of a hydroxy silicone oil, an amino silicone oil, and an alkylhydroxy silicone oil.

In a more preferred embodiment, the organosilicon compound is a hydroxy silicone oil.

The hydroxyl silicone oil is purchased from Chu eagle new material Co., Ltd, Shenzhen city.

The applicant finds that hydroxyl silicone oil is introduced into resin, and because the surface tension of the hydroxyl silicone oil is low, the hydroxyl silicone oil can be enriched on the surface layer of a film in the resin film forming process, and the regularity of a molecular chain is damaged; meanwhile, the bond energy of the hydroxyl silicone oil is high, the structure is stable and not easy to damage, and therefore the wear resistance of the UV resin is improved.

Polyhydric alcohols

In a preferred embodiment, the polyol is selected from at least one of polytetrahydrofuran ether glycol, polybutylene adipate glycol, polycarbonate diol, polyethylene glycol, ethylene glycol, butanediol.

In a preferred embodiment, the polyol is a polycarbonate diol, polyethylene glycol, ethylene glycol.

In one embodiment, the weight ratio of the polycarbonate diol, the polyethylene glycol and the ethylene glycol is (3.8-4.2): (1.2-1.8): 1.

in a preferred embodiment, the weight ratio of the polycarbonate diol to the polyethylene glycol to the ethylene glycol is 4: 1.5: 1.

in a preferred embodiment, the polycarbonate diol has a hydroxyl value of 51 to 61 mgKOH/g.

The Hydroxyl value (Hydroxyl value) in the present invention means the number of milligrams of potassium hydroxide (KOH) corresponding to the Hydroxyl group in 1g of the sample, and is represented by mgKOH/g.

In a more preferred embodiment, the polycarbonate diol is polycarbonate diol 2000.

In one embodiment, the polyethylene glycol has a hydroxyl value of greater than 15 mgKOH/g.

In a preferred embodiment, the polyethylene glycol has a viscosity of 3.0 to 11mm at 25 ℃²/s。

In a more preferred embodiment, the polyethylene glycol is selected from at least one of polyethylene glycol 1500, polyethylene glycol 2000, polyethylene glycol 4000.

In a more preferred embodiment, the polyethylene glycol is polyethylene glycol 2000.

The polycarbonate diol was purchased from southbound runfeng petrochemical company, ltd.

The polyethylene glycol was purchased from Shanghai Aladdin Biotechnology, Inc.

Nanoparticles

Nanoparticles, also called ultrafine particles, are particles with a particle size of 1-100 nm.

In one embodiment, raw materials for preparing the nanoparticles comprise graphene oxide, silicon dioxide and 4-aminobutyltriethoxysilane.

In one embodiment, the method for preparing the nanoparticles comprises at least the following steps: mixing silicon dioxide, 4-aminobutyltriethoxysilane and ethanol aqueous solution, performing ultrasonic treatment for 30-50min, stirring at 60-70 ℃ for 5-10h, adding graphene oxide, stirring for 2-4h, washing with deionized water, and freeze-drying to obtain nanoparticles.

In a preferred embodiment, the method for preparing said nanoparticles comprises at least the following steps: mixing silicon dioxide, 4-aminobutyltriethoxysilane and ethanol aqueous solution, performing ultrasonic treatment for 40min, stirring at 65 ℃ for 8h, adding graphene oxide, continuously stirring for 3h, washing with deionized water, and freeze-drying to obtain the nanoparticles.

In one embodiment, the weight ratio of the silica, the 4-aminobutyltriethoxysilane, and the aqueous ethanol solution is (2-4): 1: (5-8).

In a preferred embodiment, the weight ratio of the silica, the 4-aminobutyltriethoxysilane, and the aqueous ethanol solution is 3: 1: 6.

in one embodiment, the concentration of the aqueous ethanol solution is from 85 to 95 wt%.

In a preferred embodiment, the concentration of the aqueous ethanol solution is 90 wt%.

In a preferred embodiment, in the raw materials for preparing the nanoparticles, the average particle diameters of the graphene oxide and the silicon dioxide are respectively 20-30 nm.

In a more preferred embodiment, the average particle diameters of the graphene oxide and the silicon dioxide in the raw materials for preparing the nanoparticles are respectively 25 nm.

In a preferred embodiment, in the raw materials for preparing the nanoparticles, the weight ratio of graphene oxide to silicon dioxide is (0.06-0.1): 1.

in a more preferred embodiment, in the raw materials for preparing the nanoparticles, the weight ratio of graphene oxide to silicon dioxide is 0.08: 1.

the CAS number of the 4-aminobutyltriethoxysilane is 3069-30-5.

The graphene oxide was purchased from Nanjing Xiancheng nanomaterial science and technology Limited.

The silica was purchased from Guangzhou hundred million peaking Industrial technologies, Inc.

The introduction of the nano particles can effectively prevent the crack from extending, and when the resin coating is subjected to external acting force, the nano particles can absorb energy generated by the external acting force, so that the wear resistance of the resin is further improved.

Through a large number of experiments, the applicant finds that when the resin is prepared by using the nano particles and the average particle sizes of the graphene oxide and the silicon dioxide are controlled to be 20-30nm respectively, the prepared resin has excellent wear resistance. The applicant speculates that possible reasons are: under specific conditions, the nano particles can be uniformly dispersed in a resin matrix and play a role of crosslinking points in the resin, and active groups on the surface of the nano particles can be associated with polar groups in a system through intermolecular force on one hand, so that cohesive energy is increased; on the other hand, the resin can also react with isocyanic acid radical and the like in a system, the ordering degree of the hard segment of the resin is damaged, and the phase mixing between the soft segment and the soft segment of the resin is increased.

Acrylic acid hydroxy ester

In a preferred embodiment, the hydroxy acrylate is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate.

In a more preferred embodiment, the hydroxy acrylate is hydroxyethyl acrylate.

The hydroxyethyl acrylate has a CAS number of 818-61-1.

Neutralizing agent

The neutralizing agent is a substance for adjusting the pH value of the medium by the interaction of acid (acid salt) and alkali (basic salt).

In a preferred embodiment, the neutralizing agent is selected from at least one of monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine.

In a more preferred embodiment, the neutralizing agent is N-methyldiethanolamine.

The CAS number of the N-methyldiethanolamine is 105-59-9.

In a preferred embodiment, the preparation method of the high elasticity water-based UV resin at least comprises the following steps: mixing isocyanate, a catalyst, polyol, nano particles and an organic silicon compound, reacting at 50 ℃ for 3h, adding a polymerization inhibitor and hydroxy acrylate, reacting at 70 ℃ for 3h, adding a neutralizer and 30-40 parts by weight of water at 40 ℃, adjusting the pH value to 7, and stirring and reacting for 2h to obtain the high-elasticity waterborne UV resin.

In a more preferred embodiment, the method for preparing the high elasticity aqueous UV resin at least comprises the following steps: isocyanate, a catalyst, polyol, nano particles and an organic silicon compound are mixed and then react for 3 hours at 50 ℃, then a polymerization inhibitor and hydroxy acrylate are added to react for 3 hours at 70 ℃, then a neutralizer and 35 parts by weight of water are added at 40 ℃, the pH value is adjusted to 7, and the high-elasticity waterborne UV resin is prepared by stirring and reacting for 2 hours.

The high-elasticity water-based UV resin prepared by the invention has the advantages of both polyurethane resin and polyacrylate resin. The main chain of the high-elasticity water-based UV resin comprises a soft segment and a hard segment, wherein the soft segment is weaker in polarity, the hard segment is larger in cohesive energy, hydrogen bonds can be formed among molecules, and the soft segment and the hard segment are gathered together to form a hard segment micro-phase region. Due to the thermodynamic incompatibility of the hard phase domains and the soft phase domains, microphase separation, i.e., microphase separation, occurs. Under the condition of the same hardness, the elongation at break of the resin is determined by the soft segments and the microphase separation degree of the soft segments, the larger the microphase separation degree of the soft segments is, the larger the aggregation degree of the soft segments is, the more obvious the characteristic of the soft segments is reflected, and thus the higher elongation at break can be obtained.

Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. In addition, all the raw materials are commercially available if not particularly limited.

Examples

Example 1

The embodiment 1 of the invention provides a high-elasticity water-based UV resin which comprises the following components in parts by weight: 40 parts of isocyanate, 0.1 part of catalyst, 0.2 part of polymerization inhibitor, 30 parts of organic silicon compound, 30 parts of polyalcohol, 8 parts of nano particles, 10 parts of hydroxy acrylate and 8 parts of neutralizer.

The isocyanate is diphenylmethane diisocyanate.

The catalyst is stannous octoate.

The polymerization inhibitor is 2, 6-di-tert-butyl-p-ethylphenol.

The organic silicon compound is hydroxyl silicone oil.

The polyol is polycarbonate diol, polyethylene glycol or ethylene glycol.

The weight ratio of the polycarbonate diol to the polyethylene glycol to the ethylene glycol is 4: 1.5: 1.

the polycarbonate diol is polycarbonate diol 2000.

The polyethylene glycol is polyethylene glycol 2000.

The preparation raw materials of the nano particles comprise graphene oxide, silicon dioxide and 4-aminobutyltriethoxysilane.

The preparation method of the nano-particles comprises the following steps: mixing silicon dioxide, 4-aminobutyltriethoxysilane and ethanol aqueous solution, performing ultrasonic treatment for 40min, stirring at 65 ℃ for 8h, adding graphene oxide, continuously stirring for 3h, washing with deionized water, and freeze-drying to obtain the nanoparticles.

The weight ratio of the silicon dioxide, the 4-aminobutyltriethoxysilane to the ethanol aqueous solution is 3: 1: 6.

the concentration of the ethanol aqueous solution is 90 wt%.

The average particle sizes of the graphene oxide and the silicon dioxide are respectively 25 nm.

The weight ratio of the graphene oxide to the silicon dioxide is 0.08: 1.

the hydroxyl acrylate is hydroxyethyl acrylate.

The neutralizing agent is N-methyldiethanolamine.

The preparation method of the high-elasticity water-based UV resin comprises the following steps: isocyanate, a catalyst, polyol, nano particles and an organic silicon compound are mixed and then react for 3 hours at 50 ℃, then a polymerization inhibitor and hydroxy acrylate are added to react for 3 hours at 70 ℃, then a neutralizer and 35 parts by weight of water are added at 40 ℃, the pH value is adjusted to 7, and the high-elasticity waterborne UV resin is prepared by stirring and reacting for 2 hours.

Example 2

The embodiment 2 of the invention provides a high-elasticity water-based UV resin which comprises the following components in parts by weight: 35 parts of isocyanate, 0.05 part of catalyst, 0.1 part of polymerization inhibitor, 25 parts of organic silicon compound, 25 parts of polyol, 3 parts of nano particles, 5 parts of hydroxy acrylate and 5 parts of neutralizer.

The isocyanate is diphenylmethane diisocyanate.

The catalyst is stannous octoate.

The polymerization inhibitor is 2, 6-di-tert-butyl-p-ethylphenol.

The organic silicon compound is hydroxyl silicone oil.

The polyol is polycarbonate diol, polyethylene glycol or ethylene glycol.

The weight ratio of the polycarbonate diol to the polyethylene glycol to the ethylene glycol is 3.8: 1.2: 1.

the polycarbonate diol is polycarbonate diol 2000.

The polyethylene glycol is polyethylene glycol 2000.

The preparation method of the nano-particles comprises the following steps: mixing silicon dioxide, 4-aminobutyltriethoxysilane and ethanol aqueous solution, performing ultrasonic treatment for 30min, stirring at 60 ℃ for 10h, adding graphene oxide, continuously stirring for 4h, washing with deionized water, and freeze-drying to obtain the nanoparticles.

The weight ratio of the silicon dioxide, the 4-aminobutyltriethoxysilane to the ethanol aqueous solution is 2: 1: 5.

the concentration of the ethanol aqueous solution is 85 wt%.

The average particle sizes of the graphene oxide and the silicon dioxide are respectively 20 nm.

The weight ratio of the graphene oxide to the silicon dioxide is 0.06: 1.

the hydroxyl acrylate is hydroxyethyl acrylate.

The neutralizing agent is N-methyldiethanolamine.

The preparation method of the high-elasticity water-based UV resin comprises the following steps: mixing isocyanate, a catalyst, polyol, nano particles and an organic silicon compound, reacting at 50 ℃ for 3h, adding a polymerization inhibitor and hydroxy acrylate, reacting at 70 ℃ for 3h, adding a neutralizer and 30 parts by weight of water at 40 ℃, adjusting the pH value to 7, and stirring for reacting for 2h to obtain the high-elasticity waterborne UV resin.

Example 3

Embodiment 3 of the present invention provides a high elasticity aqueous UV resin, comprising the following components in parts by weight: 45 parts of isocyanate, 0.2 part of catalyst, 0.3 part of polymerization inhibitor, 35 parts of organic silicon compound, 35 parts of polyol, 12 parts of nano particles, 15 parts of hydroxy acrylate and 10 parts of neutralizer.

The isocyanate is diphenylmethane diisocyanate.

The catalyst is stannous octoate.

The polymerization inhibitor is 2, 6-di-tert-butyl-p-ethylphenol.

The organic silicon compound is hydroxyl silicone oil.

The polyol is polycarbonate diol, polyethylene glycol or ethylene glycol.

The weight ratio of the polycarbonate diol to the polyethylene glycol to the ethylene glycol is 4.2: 1.8: 1.

the polycarbonate diol is polycarbonate diol 2000.

The polyethylene glycol is polyethylene glycol 2000.

The preparation method of the nano-particles comprises the following steps: mixing silicon dioxide, 4-aminobutyltriethoxysilane and ethanol aqueous solution, performing ultrasonic treatment for 50min, stirring at 70 ℃ for 5h, adding graphene oxide, continuously stirring for 2h, washing with deionized water, and freeze-drying to obtain nanoparticles.

The weight ratio of the silicon dioxide, the 4-aminobutyltriethoxysilane to the ethanol aqueous solution is 4: 1: 8.

the concentration of the ethanol aqueous solution is 95 wt%.

The average particle sizes of the graphene oxide and the silicon dioxide are respectively 30 nm.

The weight ratio of the graphene oxide to the silicon dioxide is 0.1: 1.

the hydroxyl acrylate is hydroxyethyl acrylate.

The neutralizing agent is N-methyldiethanolamine.

The preparation method of the high-elasticity water-based UV resin comprises the following steps: mixing isocyanate, a catalyst, polyol, nano particles and an organic silicon compound, reacting at 50 ℃ for 3h, adding a polymerization inhibitor and hydroxy acrylate, reacting at 70 ℃ for 3h, adding a neutralizer and 40 parts by weight of water at 40 ℃, adjusting the pH value to 7, and stirring for reacting for 2h to obtain the high-elasticity waterborne UV resin.

Example 4

Embodiment 4 of the present invention provides a high elasticity aqueous UV resin, and a method for preparing the same, as in embodiment 1, except that the amount of the nanoparticles added is replaced with 0.

Example 5

The embodiment 5 of the invention provides a high-elasticity waterborne UV resin and a preparation method thereof, and the specific implementation mode is the same as that of the embodiment 1, except that:

the raw materials for preparing the nano particles comprise silicon dioxide and 4-aminobutyltriethoxysilane.

The preparation method of the nano-particles comprises the following steps: mixing silicon dioxide, 4-aminobutyltriethoxysilane and ethanol water solution, performing ultrasonic treatment for 40min, stirring at 65 ℃ for 8h, washing with deionized water, and freeze-drying to obtain nanoparticles.

the concentration of the ethanol aqueous solution is 90 wt%.

The average particle size of the silica was 25 nm.

Example 6

Example 6 of the present invention provides a highly elastic aqueous UV resin and a method for producing a highly elastic aqueous UV resin, and the specific embodiment is the same as example 1 except that the amount of the organosilicon compound added is replaced with 0.

Example 7

The embodiment 7 of the present invention provides a high elasticity aqueous UV resin and a method for preparing the same, as the embodiment 1, except that the polyol is polycarbonate diol 2000.

Example 8

The embodiment 8 of the invention provides a high-elasticity waterborne UV resin and a preparation method thereof, and the specific implementation mode is the same as that of the embodiment 1, except that the polyol is polycarbonate diol or polyethylene glycol.

Example 9

Embodiment 9 of the present invention provides a high elasticity aqueous UV resin, and a method for preparing a high elasticity aqueous UV resin, and the specific embodiment is the same as embodiment 1, except that the average particle diameters of the graphene oxide and the silicon dioxide are 10nm, respectively.

Example 10

The embodiment 10 of the invention provides a high-elasticity aqueous UV resin and a preparation method of the high-elasticity aqueous UV resin, and the specific implementation manner of the high-elasticity aqueous UV resin is the same as that of the embodiment 1, except that the average particle diameters of the graphene oxide and the silicon dioxide are respectively 50 nm.

Performance evaluation

1. Abrasion resistance test

The wear resistance test of the high-elasticity waterborne UV resin prepared in the examples 1-10 is carried out according to GB/T1768-: qualified, no obvious grinding mark exists on the surface of the coating; failure-significant wear marks on the coated surface.

2. Elasticity test

The high elasticity waterborne UV resins prepared in examples 1-10 were subjected to an elasticity test according to GB/T2567-2008, and the elasticity of the resins was measured as the elongation at break.

The results are shown in Table 1.

TABLE 1 results of performance test of highly elastic waterborne UV resins prepared in examples 1-10

	Wear resistance	Elongation at Break (%)
			Example 1	Qualified	578
Example 2	Qualified	572
			Example 3	Qualified	567
Example 4	Fail to be qualified	541
			Example 5	Fail to be qualified	545
Example 6	Fail to be qualified	556
			Example 7	Fail to be qualified	550
Example 8	Fail to be qualified	558
			Example 9	Fail to be qualified	553
Example 10	Fail to be qualified	562

The experimental result shows that the high-elasticity water-based UV resin prepared by the invention has excellent performance, excellent wear resistance and elasticity, and the elongation of the high-elasticity water-based UV resin reaches more than 500 percent.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. The use of some numerical ranges in the claims also includes sub-ranges within their range, and variations in these ranges are also to be construed as being covered by the appended claims where possible.

Claims

1. a high-elasticity water-based UV resin is characterized in that, in parts by weight, at least the following components are included: 35-45 parts of isocyanates, 0.05-0.2 parts of catalysts, 0.1-0.3 parts of polymerization inhibitors, 25-35 parts of organic silicon compounds parts, 25-35 parts of polyol, 3-12 parts of nanoparticles, 5-15 parts of hydroxy acrylate, and 5-10 parts of neutralizer;

The polyol is polycarbonate diol, polyethylene glycol, and ethylene glycol; the weight ratio of the polycarbonate diol, polyethylene glycol, and ethylene glycol is (3.8-4.2): (1.2 -1.8): 1;

The preparation raw materials of the nanoparticles include graphene oxide, silicon dioxide, and 4-aminobutyltriethoxysilane.

2 . The high-elasticity water-based UV resin according to claim 1 , wherein the catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate and triethylenediamine. 3 .

3. high elasticity water-based UV resin as claimed in claim 1 is characterized in that, described polymerization inhibitor is selected from di-tert-amyl hydroquinone, dinitro-p-cresol, dinitro-sec-butylphenol, p-tert-butylcatechol, di-tert-butyl-p-ethylphenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical, 2,2,6,6-tetramethyl At least one of the group consisting of piperidine-1-oxyl radical, p-methoxyphenol, p-hydroxyphenethyl ether, and hydroquinone.

4 . The high-elasticity water-based UV resin according to claim 1 , wherein the organosilicon compound is selected from at least one of hydroxysilicone oil, aminosilicone oil, and alkoxysilicone oil. 5 .

5 . The high-elasticity water-based UV resin according to claim 1 , wherein in the raw materials for preparing the nanoparticles, the average particle diameters of graphene oxide and silicon dioxide are respectively 20-30 nm. 6 .

6 . The high-elasticity water-based UV resin according to claim 1 , wherein in the raw materials for preparing the nanoparticles, the weight ratio of graphene oxide and silicon dioxide is (0.06-0.1):1. 7 .

7. The high-elasticity water-based UV resin according to claim 1, wherein the hydroxy acrylate is selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and glycerol dimethacrylate ester, at least one of pentaerythritol triacrylate, dipentaerythritol pentaacrylate.

8. the preparation method of the high elasticity water-based UV resin as described in any one of claim 1-7, it is characterized in that, comprise the following steps at least: mix isocyanate, catalyzer, polyhydric alcohol, nano-particle, organosilicon compound After mixing, react at 40-60℃ for 2-3h, then add polymerization inhibitor and hydroxy acrylate and react at 60-80℃ for 2-3h, then add neutralizer and water at 40-45℃ to adjust pH value To 7, stirring and reacting for 1-3h to prepare a high-elasticity water-based UV resin.