CN112064976A

CN112064976A - High-wear-resistance EB floor and preparation method thereof

Info

Publication number: CN112064976A
Application number: CN202010895301.0A
Authority: CN
Inventors: 雷响
Original assignee: Anhui Yangzi Flooring Inc Co
Current assignee: Anhui Yangzi Flooring Inc Co
Priority date: 2020-08-31
Filing date: 2020-08-31
Publication date: 2020-12-11

Abstract

The invention discloses a high-wear-resistance EB floor, which comprises a glass magnesium board base layer, a decorative layer adhered to the surface of the glass magnesium board base layer through an adhesive, a wear-resistant layer adhered to the surface of the decorative layer through the adhesive and EB (Electron beam) curing coating solidified on the surface of the wear-resistant layer through EB (Electron beam) equipment; placing carbon fibers in acetone for ultrasonic treatment twice, taking out the carbon fibers, placing the carbon fibers in deionized water for cleaning once, transferring the carbon fibers to a 5-hydroxytryptamine solution with the concentration of 1.5g/L, magnetically stirring the carbon fibers for 30min, taking out the carbon fibers, placing the carbon fibers in the deionized water for magnetic stirring for 1h, then ultrasonically oscillating the carbon fibers for 15min, taking out the carbon fibers, and drying the carbon fibers at 75 ℃ for 2h to obtain primarily treated carbon fibers; the invention also discloses a preparation method of the high-wear-resistance EB floor; the 5-hydroxytryptamine layer reacts with the KH550, the KH550 can react with polyethylene in the compounding process, and the 5-hydroxytryptamine layer and the carbon fiber can be compounded more tightly due to the synergistic effect of the KH550, the KH550 and the polyethylene.

Description

High-wear-resistance EB floor and preparation method thereof

Technical Field

The invention belongs to the technical field of floor preparation, and particularly relates to a high-wear-resistance EB floor and a preparation method thereof.

Background

In the prior art, in order to prevent abrasion, a layer of abrasion-resistant paint is usually coated on the surface of a floor, and the preparation method of the abrasion-resistant paint is to mix and dissolve abrasion-resistant emulsion and the existing common paint (such as UV paint) in a certain proportion, so that the performance of the abrasion-resistant emulsion directly influences the quality of the floor. Because the existing wear-resistant emulsion has poor intersolubility with common paint, the wear resistance of the floor coated with the wear-resistant paint is not ideal. The method commonly used for improving the wear resistance of the floor is to increase the number of coating layers of the wear-resistant paint, so that the consumption of the wear-resistant paint is greatly increased, and the production cost of the floor is improved;

the Chinese invention patent CN101666155A discloses a wear-resistant wood floor, the coating process of which is to coat six layers of common paint on the bottom surface of the wood floor, then coat a layer of common paint on the surface of the wood floor, and then coat a layer of nano wear-resistant paint on the surface of the wood floor. The paint has the advantages of excellent wear resistance, good paint adhesion and scratch resistance, low production cost, fine and uniform paint coating and attractive and harmonious appearance.

Disclosure of Invention

In order to overcome the technical problems, the invention provides a high-wear-resistance EB floor and a preparation method thereof.

The carbon fiber and the polyethylene are compounded, the interface performance between the carbon fiber and the polyethylene is poor, and the excellent combination capacity between the functional groups such as hydroxyl, amino and the like on the 5-hydroxytryptamine layer and the polyethylene cannot be achieved, the carbon fiber is treated again through KH550 in the second step, the 5-hydroxytryptamine layer reacts with the KH550, and the KH550 can react with the polyethylene in the compounding process, the 5-hydroxytryptamine layer and the carbon fiber can be compounded more tightly under the synergistic effect of the three, the carbon fiber and the polyethylene can be tightly bonded, the integral stability is improved, and the polyethylene composite material can be endowed with excellent wear resistance through the filling of the modified carbon fiber nano silica.

The purpose of the invention can be realized by the following technical scheme:

a high-wear-resistance EB floor comprises a glass magnesium board base layer, a veneer layer adhered to the surface of the glass magnesium board base layer through an adhesive, a wear-resistant layer adhered to the surface of the veneer layer through the adhesive and an EB (Electron Beam) curing coating solidified on the surface of the wear-resistant layer through EB equipment;

the decorative layer is any one of decorative paper, wood veneer and a PVC color film.

The wear-resistant layer is made of a polyethylene composite material, and the polyethylene composite material is prepared by the following method:

firstly, placing carbon fibers in acetone for ultrasonic treatment twice, wherein the first time is 20min, the second time is 10min, then taking out the carbon fibers, placing the carbon fibers in deionized water for cleaning once, transferring the carbon fibers to a 5-hydroxytryptamine solution with the concentration of 1.5g/L, magnetically stirring the carbon fibers for 30min, taking out the carbon fibers, placing the carbon fibers in the deionized water for magnetic stirring for 1h, then ultrasonically oscillating the carbon fibers for 15min, then taking out the carbon fibers, drying the carbon fibers at 75 ℃ for 2h to prepare primarily treated carbon fibers, and controlling the weight ratio of the carbon fibers to the 5-hydroxytryptamine solution to be;

secondly, adding KH550 and deionized water into a beaker, heating in a water bath at 45 ℃, stirring at a constant speed for 15min, adding the carbon fiber subjected to primary treatment in the first step, stirring for 4h by magnetic force, adding absolute ethyl alcohol, continuously stirring for 1h, ultrasonically oscillating for 10min, taking out, and drying at 60 ℃ to obtain modified carbon fiber;

and step three, uniformly mixing the prepared modified carbon fibers and nano silicon dioxide, uniformly mixing the mixture with ultrahigh molecular weight polyethylene, and pressing and vulcanizing the mixture to obtain the polyethylene composite material.

In the first step, carbon fibers are placed in acetone and cleaned after ultrasonic treatment, the surfaces of the carbon fibers in the market are coated with a sizing agent to protect the carbon fibers, but the sizing agent is introduced into a weak interface layer while protecting the carbon fibers, so that acetone and deionized water are required to be used for cleaning, the 5-hydroxytryptamine solution is guaranteed to be capable of efficiently treating the surfaces of the carbon fibers, then the carbon fibers are transferred into the 5-hydroxytryptamine solution, a uniform 5-hydroxytryptamine layer is formed on the surfaces of the carbon fibers, on one hand, the roughness of the surfaces of the carbon fibers can be increased, and on the other hand, active functional groups can be introduced into; the carbon fiber and the polyethylene are compounded, the interface performance between the carbon fiber and the polyethylene is poor, and the excellent combination capacity between the functional groups such as hydroxyl, amino and the like on the 5-hydroxytryptamine layer and the polyethylene cannot be achieved, the carbon fiber is treated again through KH550 in the second step, the 5-hydroxytryptamine layer reacts with the KH550, and the KH550 can react with the polyethylene in the compounding process, the 5-hydroxytryptamine layer and the carbon fiber can be compounded more tightly under the synergistic effect of the three, the carbon fiber and the polyethylene can be tightly bonded, the integral stability is improved, and the polyethylene composite material can be endowed with excellent wear resistance through the filling of the modified carbon fiber nano silica.

Further, in the second step, the weight ratio of the carbon fiber after the primary treatment, the KH550, the deionized water and the absolute ethyl alcohol is controlled to be 5: 1: 5-6.

Further, the EB cured coating is made by the following method:

step S1, adding novolac epoxy resin into a three-neck flask, adding toluene, magnetically stirring for 15-20min, adding N, N-dimethylformamide, continuously stirring for 5min to obtain a mixed solution A, mixing p-hydroxyanisole, acrylic acid and toluene to obtain a mixed solution B, dripping the mixed solution B into the mixed solution A, controlling the dripping time to be 25-30min, reacting at 75 ℃, 80 ℃, 85 ℃ and 90 ℃ for 15min respectively after dripping is finished, detecting the acid value of a system, stopping the reaction until the acid value is less than 0.5mgKOH/g, extracting with anhydrous ether for three times, drying at 45-50 ℃ for 20h to obtain a first intermediate, and controlling the weight ratio of the mixed solution B to the mixed solution A to be 8-10: 1;

step S2, adding toluene diisocyanate into a four-neck flask filled with tetrahydrofuran, placing the flask in an ice-water bath, magnetically stirring for 30min, then dripping KH560, controlling the dripping time to be 30min, preparing a modifier, adding a first intermediate into the tetrahydrofuran, magnetically stirring for 20min, then sequentially adding dimethyltin and hydroxyanisole, stirring for 30min at a rotating speed of 120r/min, then adding the modifier, uniformly stirring at a rotating speed of 200r/min, reacting for 4h, and then preparing a second intermediate, controlling the weight ratio of the toluene diisocyanate to the KH560 to the tetrahydrofuran to be 1: 10, and controlling the weight ratio of the first intermediate to the tetrahydrofuran to be 1: 15: 0.01: 0.1: 0.5;

and step S3, mixing the heat-conducting and heat-dissipating filler and the auxiliary agent with the second intermediate, grinding to obtain the EB curing coating, and controlling the weight ratio of the second intermediate to the heat-conducting and heat-dissipating filler to the auxiliary agent to be 3: 2: 0.5.

Further, the weight ratio of the novolac epoxy resin, the toluene and the N, N-dimethylformamide is controlled to be 1: 5: 0.01-0.02, and the weight ratio of the p-hydroxyanisole, the acrylic acid and the toluene is controlled to be 1: 2.

Further, the heat-conducting and heat-dissipating filler is one of carbon black and graphite, and the auxiliary agent is formed by mixing a dispersing agent and a flatting agent according to the weight ratio of 1: 1.

A preparation method of a high-wear-resistance EB floor comprises the following steps:

and adhering the wear-resistant layer to the surface of the glass magnesium board substrate by using an adhesive, and then solidifying the EB curing coating on the surface of the wear-resistant layer by using EB equipment.

Step S1, mixing novolac epoxy resin with toluene, adding N, N-dimethylformamide as a catalyst to prepare a mixed solution A, mixing p-hydroxyanisole with acrylic acid, adding the mixed solution A, wherein the acrylic acid can perform ring-opening modification on the novolac epoxy resin, and grafting double bonds capable of being directly cured by electron beams into the novolac epoxy resin to prepare a first intermediate; in step S2, a modifier is prepared from toluene diisocyanate and KH560, then the first intermediate and the modifier react under the action of a catalyst such as dimethyl tin, the toluene diisocyanate and KH560 can graft and modify hydroxyl groups on side chains of the first intermediate to prepare a second intermediate, and then in step S3, the second intermediate, the heat-conducting and heat-dissipating filler and the auxiliary agent are mixed and ground to prepare the EB cured coating.

The invention has the beneficial effects that:

(1) the invention relates to a high-wear-resistance EB floor, which comprises a glass magnesium board base layer, a veneer layer adhered to the surface of the glass magnesium board base layer through an adhesive, a wear-resistant layer adhered to the surface of the veneer layer through the adhesive and EB (Electron beam) curing coating solidified on the surface of the wear-resistant layer through EB equipment, wherein the wear-resistant layer is a polyethylene composite material, in the first step in the preparation process, carbon fibers are placed in acetone for ultrasonic cleaning, the surfaces of the carbon fibers in the market are coated with a sizing agent for protecting the carbon fibers, but the sizing agent can be introduced into a weak interface layer while protecting the carbon fibers, so that acetone and deionized water are required for cleaning, the 5-hydroxytryptamine solution can be used for efficiently treating the surfaces of the carbon fibers, then the carbon fibers are transferred into the 5-hydroxytryptamine solution, a uniform 5-hydroxytryptamine layer is formed on the, on the other hand, active functional groups can be introduced on the surface of the carbon fiber; the carbon fiber and the polyethylene are compounded, the interface performance between the carbon fiber and the polyethylene is poor, and the excellent combination capacity between the functional groups such as hydroxyl, amino and the like on the 5-hydroxytryptamine layer and the polyethylene cannot be achieved, the carbon fiber is treated again through KH550 in the second step, the 5-hydroxytryptamine layer reacts with the KH550, and the KH550 can react with the polyethylene in the compounding process, the 5-hydroxytryptamine layer and the carbon fiber can be compounded more tightly under the synergistic effect of the three, the carbon fiber and the polyethylene can be tightly bonded, the integral stability is improved, and the polyethylene composite material can be endowed with excellent wear resistance through the filling of the modified carbon fiber nano silica.

(2) In the preparation process of the EB curing coating, in the step S1, phenolic epoxy resin and toluene are mixed, then N, N-dimethylformamide is added as a catalyst to prepare a mixed solution A, p-hydroxyanisole and acrylic acid are mixed, then the mixed solution A is added, the acrylic acid can perform ring-opening modification on the phenolic epoxy resin, and double bonds capable of being directly cured by electron beams are accessed into the phenolic epoxy resin to prepare a first intermediate; in step S2, a modifier is prepared from toluene diisocyanate and KH560, then the first intermediate and the modifier react under the action of a catalyst such as dimethyl tin, the toluene diisocyanate and KH560 can graft and modify hydroxyl groups on side chains of the first intermediate to prepare a second intermediate, and then in step S3, the second intermediate, the heat-conducting and heat-dissipating filler and the auxiliary agent are mixed and ground to prepare the EB cured coating.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

firstly, placing carbon fibers in acetone for ultrasonic treatment twice, wherein the first time is 20min, the second time is 10min, then taking out the carbon fibers, placing the carbon fibers in deionized water for cleaning once, transferring the carbon fibers to a 5-hydroxytryptamine solution with the concentration of 1.5g/L, magnetically stirring the carbon fibers for 30min, taking out the carbon fibers, placing the carbon fibers in the deionized water for magnetic stirring for 1h, then ultrasonically oscillating the carbon fibers for 15min, then taking out the carbon fibers, drying the carbon fibers at 75 ℃ for 2h to prepare primarily treated carbon fibers, and controlling the weight ratio of the carbon fibers to the 5-hydroxytryptamine solution;

secondly, adding KH550 and deionized water into a beaker, heating in a water bath at 45 ℃, uniformly stirring for 15min, adding the carbon fiber subjected to primary treatment in the first step, magnetically stirring for 4h, adding absolute ethyl alcohol, continuously stirring for 1h, ultrasonically oscillating for 10min, taking out, drying at 60 ℃ to obtain modified carbon fiber, and controlling the weight ratio of the carbon fiber subjected to primary treatment to KH550 to the deionized water to the absolute ethyl alcohol to be 5: 1: 5;

The EB curing coating is prepared by the following method:

step S1, adding novolac epoxy resin into a three-neck flask, adding toluene, magnetically stirring for 15min, adding N, N-dimethylformamide, continuously stirring for 5min to obtain a mixed solution A, mixing p-hydroxyanisole, acrylic acid and toluene to obtain a mixed solution B, dripping the mixed solution B into the mixed solution A, controlling the dripping time to be 25min, reacting at 75 ℃, 80 ℃, 85 ℃ and 90 ℃ for 15min respectively after finishing dripping, detecting the acid value of a system, stopping the reaction until the acid value is less than 0.5mgKOH/g, extracting with anhydrous ether for three times, drying at 45 ℃ for 20h to obtain a first intermediate, controlling the weight ratio of the novolac epoxy resin to the toluene to the N, N-dimethylformamide to be 1: 5: 0.01, the weight ratio of the p-hydroxyanisole, the acrylic acid and the toluene is 1: 2, and the weight ratio of the mixed solution B to the mixed solution A is controlled to be 8: 1;

and step S3, mixing the carbon black and the auxiliary agent with the second intermediate, grinding to obtain the EB curing coating, and controlling the weight ratio of the second intermediate, the carbon black and the auxiliary agent to be 3: 2: 0.5.

The auxiliary agent is formed by mixing triethyl hexyl phosphoric acid and polydimethylsiloxane according to the weight ratio of 1: 1.

Example 2

secondly, adding KH550 and deionized water into a beaker, heating in a water bath at 45 ℃, uniformly stirring for 15min, adding the carbon fiber subjected to primary treatment in the first step, magnetically stirring for 4h, adding absolute ethyl alcohol, continuously stirring for 1h, ultrasonically oscillating for 10min, taking out, drying at 60 ℃ to obtain modified carbon fiber, and controlling the weight ratio of the carbon fiber subjected to primary treatment to KH550 to the deionized water to the absolute ethyl alcohol to be 5: 1: 5: 6;

The EB curing coating is prepared by the following method:

step S1, adding novolac epoxy resin into a three-neck flask, adding toluene, magnetically stirring for 15min, adding N, N-dimethylformamide, continuously stirring for 5min to obtain a mixed solution A, mixing p-hydroxyanisole, acrylic acid and toluene to obtain a mixed solution B, dripping the mixed solution B into the mixed solution A, controlling the dripping time to be 25min, reacting at 75 ℃, 80 ℃, 85 ℃ and 90 ℃ for 15min respectively after finishing dripping, detecting the acid value of a system, stopping the reaction until the acid value is less than 0.5mgKOH/g, extracting with anhydrous ether for three times, drying at 45 ℃ for 20h to obtain a first intermediate, controlling the weight ratio of the novolac epoxy resin to the toluene to the N, N-dimethylformamide to be 1: 5: 0.01, the weight ratio of the p-hydroxyanisole, the acrylic acid and the toluene is 1: 2, and the weight ratio of the mixed solution B to the mixed solution A is controlled to be 10: 1;

Example 3

secondly, adding KH550 and deionized water into a beaker, heating in a water bath at 45 ℃, uniformly stirring for 15min, adding the carbon fiber subjected to primary treatment in the first step, magnetically stirring for 4h, adding absolute ethyl alcohol, continuously stirring for 1h, ultrasonically oscillating for 10min, taking out, drying at 60 ℃ to obtain modified carbon fiber, and controlling the weight ratio of the carbon fiber subjected to primary treatment to KH550 to the deionized water to the absolute ethyl alcohol to be 5: 1: 6;

The EB curing coating is prepared by the following method:

step S1, adding novolac epoxy resin into a three-neck flask, adding toluene, magnetically stirring for 15min, adding N, N-dimethylformamide, continuously stirring for 5min to obtain a mixed solution A, mixing p-hydroxyanisole, acrylic acid and toluene to obtain a mixed solution B, dripping the mixed solution B into the mixed solution A, controlling the dripping time to be 25min, reacting at 75 ℃, 80 ℃, 85 ℃ and 90 ℃ for 15min respectively after finishing dripping, detecting the acid value of a system, stopping the reaction until the acid value is less than 0.5mgKOH/g, extracting with anhydrous ether for three times, drying at 45 ℃ for 20h to obtain a first intermediate, controlling the weight ratio of the novolac epoxy resin to the toluene to the N, N-dimethylformamide to be 1: 5: 0.02, the weight ratio of the p-hydroxyanisole, the acrylic acid and the toluene is 1: 2, and the weight ratio of the mixed solution B to the mixed solution A is controlled to be 8: 1;

Example 4

The EB curing coating is prepared by the following method:

step S1, adding novolac epoxy resin into a three-neck flask, adding toluene, magnetically stirring for 15min, adding N, N-dimethylformamide, continuously stirring for 5min to obtain a mixed solution A, mixing p-hydroxyanisole, acrylic acid and toluene to obtain a mixed solution B, dripping the mixed solution B into the mixed solution A, controlling the dripping time to be 25min, reacting at 75 ℃, 80 ℃, 85 ℃ and 90 ℃ for 15min respectively after finishing dripping, detecting the acid value of a system, stopping the reaction until the acid value is less than 0.5mgKOH/g, extracting with anhydrous ether for three times, drying at 45 ℃ for 20h to obtain a first intermediate, controlling the weight ratio of the novolac epoxy resin to the toluene to the N, N-dimethylformamide to be 1: 5: 0.02, the weight ratio of the p-hydroxyanisole, the acrylic acid and the toluene is 1: 2, and the weight ratio of the mixed solution B to the mixed solution A is controlled to be 10: 1;

Comparative example 1

In this comparative example, the abrasion resistant layer was low density polyethylene as compared to example 1.

Comparative example 2

This comparative example compares to example 1 without EB cured coating.

Comparative example 3

This comparative example is a high wear-resistant EB floor in the market.

The abrasion resistance and mechanical properties of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table;

	amount of wear (kg/m)²)	Compressive strength MPa	Interface bonding strength MPa
				Example 1	0.18	168	220
Example 2	0.16	166	218
				Example 3	0.15	165	220
Example 4	0.15	166	221
				Comparative example 1	0.45	154	215
Comparative example 2	0.22	152	216
				Comparative example 3	0.25	150	210

As can be seen from the above table, the abrasion loss of examples 1 to 4 was 0.15 to 0.18 (kg/m)²) The compressive strength was 165-168MPa, the interface bonding strength was 218-220MPa, and the amount of abrasion was 0.22-0.45 (kg/m) for comparative examples 1-3²) The compressive strength is 150-154MPa, and the interface bonding strength is 210-216 MPa; so handle the carbon fiber once more through KH550, 5-hydroxytryptamine layer and KH550 take place the reaction, KH550 can react with polyethylene in the complex process moreover, synergistic effect between the three can enough make the complex between 5-hydroxytryptamine layer and the carbon fiber inseparabler, can make carbon fiber and polyethylene closely adhere again, promote holistic stability can, fill through modified carbon fiber and nanometer silica, can give the excellent wear resistance who makes polyethylene combined material.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims

1. The high-wear-resistance EB floor is characterized by comprising a glass magnesium board base layer, a veneer layer adhered to the surface of the glass magnesium board base layer through an adhesive, a wear-resistant layer adhered to the surface of the veneer layer through the adhesive and EB (Electron Beam) curing coating solidified on the surface of the wear-resistant layer through EB equipment;

2. The EB floor board with high abrasion resistance according to claim 1, wherein in the second step, the weight ratio of the carbon fiber after the primary treatment, the KH550, the deionized water and the absolute ethyl alcohol is controlled to be 5: 1: 5-6.

3. The EB floor of claim 1, wherein the EB cured coating is prepared by a method comprising:

4. The EB floor with high abrasion resistance according to claim 3, wherein the weight ratio of the novolac epoxy resin, the toluene and the N, N-dimethylformamide is controlled to be 1: 5: 0.01-0.02, and the weight ratio of the p-hydroxyanisole, the acrylic acid and the toluene is controlled to be 1: 2.

5. The EB floor board with high wear resistance as claimed in claim 3, wherein the heat conducting and dissipating filler is one of carbon black and graphite, and the auxiliary agent is a mixture of a dispersant and a leveling agent in a weight ratio of 1: 1.

6. The method for preparing the high-abrasion EB floor board as claimed in claim 1, wherein the method comprises the following steps:

and adhering the facing layer to the surface of the glass magnesium board substrate layer through an adhesive, adhering the wear-resistant layer to the surface of the facing layer through the adhesive, and finally solidifying the EB curing coating on the surface of the wear-resistant layer through EB equipment.