Preparation method of permanent antibacterial acrylic bathroom board

Abstract

The invention discloses a preparation method of a permanent antibacterial acrylic bathroom board. The preparation method comprises the following steps: step 1, performing prepolymerization on materials including methyl methacrylate, hydroxyl-terminated acrylate, a phosphate-terminated monomer and a high-temperature initiator to obtain an acrylic prepolymer; step 2, pre-dispersing an antibacterial agent to obtain antibacterial agent slurry; 3, uniformly mixing the materials including the acrylic prepolymer, the antibacterial agent slurry, the multifunctional acrylate cross-linking agent and the low-temperature initiator; 4, pouring into a glass mold, heating in a water bath at 60 DEG C until the edge is hardened, and then baking at 120 DEG C for 2-3 hours; and 5, cooling to normal temperature, and demolding to obtain the permanent antibacterial acrylic plate capable of being used for the bathroom product. The preparation method has the effects that the dispersity, firmness, mechanical property and water resistance of the antibacterial agent are improved through copolymerization of the methyl methacrylate, the hydroxyl-terminated acrylate monomer and the phosphate-terminated acrylate monomer, and the antibacterial agent slurry is obtained through a specific pre-dispersion formula and process.

Description

Technical Field

[0001] The invention relates to the technical field of bathroom board preparation, in particular to a method for preparing a permanent antibacterial acrylic bathroom board. Background Art

[0002] With the frequent appearance of the new coronavirus, influenza virus, and various infectious bacteria, people's attention to health and epidemic prevention is increasing, and the demand for various antibacterial and antiviral products is also increasing rapidly. Acrylic products are widely used in construction, furniture, sanitary products, interior decoration, medical equipment, automotive instruments, industrial control instruments and other applications that may come into contact with the skin. The demand for antibacterial acrylic is also increasing;

[0003] At present, many technical solutions for permanent antibacterial acrylic sheets have been published, most of which are some silver ion antibacterial agents, which are added to acrylic materials by physical blending; however, when used for bathroom materials, the sheet needs to be processed at high temperature and stretched. If the antibacterial agent is unevenly dispersed in the sheet, the stretched sheet surface will have appearance defects such as bumps, bubbles, and spots, or processing problems such as cracks and breaks; at the same time, since the addition of antibacterial agents will affect the mechanical properties, water resistance, and heat resistance of acrylic sheets, it is necessary to modify the formula of acrylic sheets while adding antibacterial agents to reduce other performance losses. The existing acrylic sheets have poor use effects and cannot meet people's needs;

[0004] In view of the above situation, it is necessary to improve the existing acrylic sheet so that it can adapt to the current needs of using acrylic sheet. Summary of the invention

[0005] To achieve the above object, the technical solution of the present invention is a method for preparing a permanent antibacterial acrylic bathroom board, comprising the following steps:

[0006] Step 1: Prepolymerizing materials including methyl methacrylate, terminal hydroxyl acrylate, terminal phosphate monomer, and high temperature initiator to obtain acrylic prepolymer;

[0007] Step 2: Pre-dispersing the antimicrobial agent to obtain an antimicrobial agent slurry;

[0008] Step 3: uniformly mix the materials including acrylic prepolymer, antimicrobial agent slurry, multifunctional acrylate crosslinking agent, and low-temperature initiator;

[0009] Step 4: Pour into a glass mold, heat in a 60℃ water bath until the edges harden, then bake at 120℃ for 2-3 hours;

[0010] Step 5: Cool to room temperature, demould, and obtain a permanent antibacterial acrylic sheet that can be used for bathroom products.

[0011] To further supplement the technical solution, the acrylic prepolymer is added in a ratio of 100 parts of methyl methacrylate, 1-3 parts of terminal hydroxyl acrylate, 0.1-0.5 parts of terminal phosphate monomer, and 0.001-0.003 parts of high-temperature initiator, and is prepolymerized by heating at 80-105°C for 30-60 minutes. The room temperature viscosity of the prepolymer is 300-1000CPS.

[0012] To further supplement the technical solution, the preparation method of the antibacterial agent slurry is: the ratio of the antibacterial agent to the dispersant is 1:0.03 to 1:0.10, and the order of adding materials is: first add the acrylic prepolymer into the mixing barrel, the stirring speed is 1000-2000 rpm, then add the dispersant, stir evenly, and then slowly add the antibacterial agent powder while stirring. After the feeding is completed, continue stirring for 3 hours, and obtain the antibacterial agent slurry after filtering through a 1000 mesh filter.

[0013] To further supplement the technical solution, the addition ratio of acrylic prepolymer, antibacterial agent slurry, multifunctional acrylate crosslinker, and low-temperature initiator in step three is: 100 parts of the total amount of acrylic prepolymer (including acrylic prepolymer in the preparation of antibacterial agent slurry), 0.3-0.6 parts of antibacterial agent, 0.01-0.05 parts of multifunctional acrylate crosslinker, 0.01-0.05 parts of low-temperature initiator, mix and stir evenly, vacuum and remove bubbles. If the viscosity of the prepolymer is too high, it is difficult to remove bubbles. If the viscosity is too low, it is easy to precipitate.

[0014] As a further supplement to the technical solution, the terminal hydroxyl acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxymethyl methacrylate.

[0015] As a further supplement to the technical solution, the terminal phosphate monomer is one or more of methacryloyloxyethyl ester, methacryloyloxyethyl ester, methacryloyloxyethyl ester, acryloyloxyethyl ester, acryloyloxyethyl ester, acryloyloxyethyl ester, methacryloyloxyethyl ester, diethyl acryloyloxyethyl ester, and diethyl acryloyloxyethyl ester.

[0016] As a further supplement to the technical solution, the high-temperature initiator is any one of azobisisobutyronitrile, benzoyl peroxide, di(4-methylbenzoyl) peroxide, tri-pentyl peroxide-2-ethylhexanoate, and tert-butyl peroxide-2-ethylhexanoate.

[0017] In a further supplement to the technical solution, the antibacterial agent is a silver ion antibacterial agent.

[0018] As a further supplement to the technical solution, the multifunctional acrylate cross-linking agent is any one of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, triisocyanuric acid triacrylate, and trimethylolpropane triacrylate.

[0019] As a further supplement to the technical solution, the low-temperature initiator is any one of azobisisoheptanenitrile, diisobutyryl peroxide, isopropyl peroxyneodecanoate, and bis(3-methoxybutyl)peroxydicarbonate.

[0020] The beneficial effect lies in that the present invention provides a method for preparing a permanent antibacterial acrylic bathroom board, wherein the dispersibility and firmness of the antibacterial agent are improved by copolymerizing methyl methacrylate, terminal hydroxyl acrylate monomer, and terminal phosphate acrylate monomer, and an antibacterial agent slurry is obtained by a specific pre-dispersion formula and process; before casting the board, a multifunctional acrylate cross-linking agent is added to improve the mechanical properties and water resistance; and a permanent antibacterial acrylic board for bathroom products is obtained. DETAILED DESCRIPTION

[0021] In order to make the technical solution more clear to those skilled in the art, the technical solution of the present invention will be described in detail below:

[0022] A method for preparing a permanent antibacterial acrylic bathroom board comprises the following steps:

[0023] Step 1: Prepolymerizing materials including methyl methacrylate, terminal hydroxyl acrylate, terminal phosphate monomer, and high temperature initiator to obtain acrylic prepolymer;

[0024] Step 2: Pre-dispersing the antimicrobial agent to obtain an antimicrobial agent slurry;

[0025] Step 3: uniformly mix the materials including acrylic prepolymer, antimicrobial agent slurry, multifunctional acrylate crosslinking agent, and low-temperature initiator;

[0026] Step 4: Pour into a glass mold, heat in a 60℃ water bath until the edges harden, then bake at 120℃ for 2-3 hours;

[0027] Step 5: Cool to room temperature, demould, and obtain a permanent antibacterial acrylic sheet that can be used for bathroom products.

[0028] The acrylic prepolymer is added in the proportion of 100 parts of methyl methacrylate, 1-3 parts of terminal hydroxyl acrylate, 0.1-0.5 parts of terminal phosphate monomer, and 0.001-0.003 parts of high-temperature initiator, and is prepolymerized by heating at 80-105° C. for 30-60 minutes. The room temperature viscosity of the prepolymer is 300-1000 CPS.

[0029] Among them, the preparation method of the antibacterial agent slurry is: the ratio of the antibacterial agent to the dispersant is 1:0.03 to 1:0.10, and the adding order is: first add the acrylic prepolymer into the stirring barrel, the stirring speed is 1000-2000 rpm, and then add the dispersant, stir evenly, and then slowly add the antibacterial agent powder while stirring. After the feeding is completed, continue stirring for 3 hours, and obtain the antibacterial agent slurry after filtering through a 1000 mesh filter.

[0030] Among them, the addition ratio of acrylic prepolymer, antibacterial agent slurry, multifunctional acrylate crosslinker, and low-temperature initiator in step three is: 100 parts of the total amount of acrylic prepolymer (including the acrylic prepolymer in the preparation of the antibacterial agent slurry), 0.3-0.6 parts of antibacterial agent, 0.01-0.05 parts of multifunctional acrylate crosslinker, 0.01-0.05 parts of low-temperature initiator, mix and stir evenly, vacuum and remove bubbles, if the viscosity of the prepolymer is too high, it is difficult to remove bubbles, if the viscosity is too low, it is easy to precipitate.

[0031] The terminal hydroxy acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxymethyl methacrylate.

[0032] Among them, the terminal phosphate monomer is one or more of mono(methacryloyloxyethyl) phosphate, di(methacryloyloxyethyl) phosphate, tri(methacryloyloxyethyl) phosphate, mono(acryloyloxyethyl) phosphate, di(acryloyloxyethyl) phosphate, tri(acryloyloxyethyl) phosphate, diethyl (methacryloyloxyethyl) phosphate, and diethyl (acryloyloxyethyl) phosphate.

[0033] The high temperature initiator is any one of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), di(4-methylbenzoyl) peroxide, tri-pentyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate.

[0034] Among them, the antibacterial agent is a silver ion antibacterial agent.

[0035] The multifunctional acrylate crosslinking agent is any one of pentaerythritol tetraacrylate (Changxing EM241), dipentaerythritol hexaacrylate (Changxing EM263), tris(2-hydroxyethyl)isocyanuric acid triacrylate (Changxing EM2308), and trimethylolpropane triacrylate (Changxing EM231).

[0036] The low-temperature initiator is any one of azobisisoheptanenitrile (ADVN), diisobutyryl peroxide (DIPB), cumyl peroxyneodecanoate (CPND), and bis(3-methoxybutyl) peroxydicarbonate.

[0037] In the embodiments of the present invention, methyl methacrylate is referred to as MMA, CAS registration number 80-62-6

[0038] The hydroxy-terminated acrylate in the embodiment of the present invention is hydroxyethyl methacrylate, referred to as HEMA, CAS registration number 868-77-9;

[0039] In the embodiment of the present invention, the terminal phosphate monomer, Sartomer SR9050 is mono(methacryloyloxyethyl) phosphate, and Changxing EM39 is a mixture of mono(methacryloyloxyethyl) phosphate and di(methacryloyloxyethyl) phosphate;

[0040] In the embodiment of the present invention, the antibacterial agent is a silver ion antibacterial agent, and in the embodiment, BC 11-01, BCA 21-61; The cost of antimicrobial agents is relatively high, and excessive addition will increase the cost, and the performance of the board will decrease after excessive addition.

[0041] The dispersant in the embodiment of the present invention is Lubrizol 24000;

[0042] In the embodiment of the present invention, an ultraviolet absorber, Suqian Liansheng UV329, is added when preparing the ingredients before board making, with an addition amount of 0.1-0.5 parts;

[0043] In the embodiment of the present invention, an antioxidant, high temperature resistant antioxidant Revonox 608, is added when preparing the ingredients before board making, with an addition amount of 0.1-0.5 parts;

[0044] Example

[0045] The following are the formulas of 5 kinds of acrylic prepolymers, see the table below for details:

[0046]

[0047]

[0048] The process conditions and room temperature viscosity of the five acrylic prepolymers are shown in the table below:

[0049] project Prepolymer 1 Prepolymer 2 Prepolymer 3 Prepolymer 4 Prepolymer 5 Reaction temperature 80℃ 95℃ 105℃ 95℃ 95℃ Pre-gathering time 30min 60min 45min 60min 60min Viscosity at room temperature 331cps 986cps 662cps 708cps 826cps

[0050] The following lists the proportions of 5 kinds of antimicrobial slurries and the phenomena after standing:

[0051]

[0052] Note: In the antimicrobial slurry, the antimicrobial agent accounts for about 50%;

[0053] The formula for making antibacterial bathroom panels using the above 5 types of acrylic prepolymers and antibacterial agent slurry is as follows:

[0054]

[0055]

[0056] Note: In the antimicrobial slurry, the antimicrobial agent accounts for about 50%;

[0057] After the materials of Examples 1-5 above are stirred evenly, 2 kg of the antibacterial acrylic mixed slurry is kept in a beaker and allowed to stand for 48 hours to observe whether it is precipitated. The remaining material is injected into a 3 mm glass mold, and the mold is placed in a 60°C water bath and heated for 3 hours, then taken out, placed in a 120°C water bath and heated for 2 hours, and demolded after cooling to obtain an antibacterial acrylic bathroom board.

[0058] The performance data of the antibacterial acrylic bathroom panels of Examples 1-5 and the phenomenon of static sedimentation of the ingredients are shown in the following table:

[0059]

[0060] Five comparative antibacterial bathroom panels were prepared using the above five acrylic prepolymers and antibacterial agent slurries. The formulas are as follows:

[0061]

[0062]

[0063] Note: In the antimicrobial slurry, the antimicrobial agent accounts for about 50%;

[0064] The antibacterial acrylic mixed slurry prepared by stirring the materials in the above comparative examples 1-5 evenly was kept in a beaker with 2 kg of the mixture left and allowed to stand for 48 hours to observe whether it precipitated. The remaining material was injected into a 3 mm glass mold, and the mold was placed in a 60°C water bath and heated for 3 hours, then taken out, placed in a 120°C water bath and heated for 2 hours, and demolded after cooling to obtain an antibacterial acrylic bathroom board.

[0065] The performance data of the antibacterial acrylic bathroom panels of Comparative Examples 1-5 and the phenomenon of static precipitation of the ingredients are shown in the following table:

[0066] Observation Project Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 The mixed slurry was left to stand for 48 hours Layering Unstratified Rockwell hardness / HRM / 86 <![CDATA[Izod impact strength / KJ / m 2 > / 18.1 Tensile strength / MPa / 61 Elongation at break / % / 4.3 Tensile elastic modulus / MPa / 2606 Vicat softening point / ℃ / 91 Hot water resistance / Gray Label 2 Degree of crosslinking / qualified Water absorption / mg / 67 Blister test / No abnormality Surface appearance after blister forming / No abnormality Escherichia coli antibacterial rate / 99.6％ Antibacterial rate of Staphylococcus aureus / 99.7％

[0067] From the comparison between Example 2 and Comparative Example 1, it can be seen that when no terminal hydroxyl acrylate and terminal phosphate acrylate are added to the acrylic prepolymer, the dispersion effect of the antibacterial agent becomes poor, and precipitation occurs after the ingredients are left to stand for 48 hours.

[0068] From the comparison between Example 2 and Comparative Example 2, it can be seen that when the antibacterial agent slurry is prepared, excessive addition of dispersant will lead to decreased mechanical properties, decreased water resistance and decreased heat resistance of the final board.

[0069] Among them, the performance test method of antibacterial bathroom panels:

[0070] 1. Rockwell hardness, GB / T 3398.2;

[0071] 2. Unnotched impact strength, GB / T 1043.1;

[0072] 3. Tensile strength, GB / T 1040;

[0073] 4. Elongation at break, GB / T 1040;

[0074] 5. Tensile elastic modulus, GB / T 1040;

[0075] 6. Vicat softening point, GB / T 1633;

[0076] 7. Hot water resistance, EN263:2008, Section 3.6.2, gray scale grade ≥3 is qualified;

[0077] 8. Degree of cross-linking, EN263:2008, Section 4.6, after the standard sample is immersed in MMA for 16 hours, if there is no dissolution and adhesion, it is qualified;

[0078] 9. Water absorption, EN263:2008, Section 4.7, according to the common industry requirements, 50mm×50mm sample, water absorption ≤40mg;

[0079] 10. For the blister test, take a 1m×1m sample, heat it at 200℃ for 15 minutes, and then put it into a mold with an inner cavity size of 0.8m×0.8m×0.8m, and blister it to observe whether there is any crack, and whether there are any convexities, depressions or bubbles on the surface;

[0080] 11. Antibacterial test, standard ISO 22196, test bacteria are: Escherichia coli (ATCC 8739) and Staphylococcus aureus (ATCC 6538P), antibacterial rate (%) calculation formula: (BC) / B×100%;

[0081] B: Average bacterial count (cells / cm2) of blank sample (untreated control sample) after 24 hours of inoculation 2 )

[0082] C: Average bacterial count of the test sample after 24 hours of inoculation (cells / cm 2 ).

[0083] The above technical solutions only reflect the preferred technical solutions of the technical solutions of the present invention. Some changes that may be made to certain parts thereof by technicians in this technical field all reflect the principles of the present invention and fall within the protection scope of the present invention.

Claims

1. A method for preparing a permanent antibacterial acrylic bathroom board, characterized in that: The following steps are involved: Step 1: Prepolymerizing materials including methyl methacrylate, terminal hydroxyl acrylate, terminal phosphate monomer, and high temperature initiator to obtain acrylic prepolymer; Step 2: Pre-dispersing the antimicrobial agent to obtain an antimicrobial agent slurry; Step 3: uniformly mix the materials including acrylic prepolymer, antimicrobial agent slurry, multifunctional acrylate crosslinking agent, and low-temperature initiator; Step 4: Pour into a glass mold, heat in a 60℃ water bath until the edges harden, then bake at 120℃ for 2-3 hours; Step 5: Cool to room temperature, demould, and obtain a permanent antibacterial acrylic sheet that can be used for bathroom products.

2. The method for preparing a permanent antibacterial acrylic bathroom board according to claim 1, characterized in that: The acrylic prepolymer is added in the proportion of 100 parts of methyl methacrylate, 1-3 parts of terminal hydroxyl acrylate, 0.1-0.5 parts of terminal phosphate monomer, and 0.001-0.003 parts of high-temperature initiator, and is prepolymerized by heating at 80-105° C. for 30-60 minutes. The room temperature viscosity of the prepolymer is 300-1000 CPS.

3. The method for preparing a permanent antibacterial acrylic bathroom board according to claim 1, characterized in that: The preparation method of the antibacterial agent slurry is: the ratio of the antibacterial agent to the dispersant is 1:0.03 to 1:0.10, and the adding order is: firstly add the acrylic prepolymer into the stirring barrel, the stirring speed is 1000-2000 rpm, then add the dispersant, stir evenly, and then slowly add the antibacterial agent powder while stirring, after the feeding is completed, continue to stir for 3 hours, and obtain the antibacterial agent slurry after filtering through a 1000-mesh filter.

4. The method for preparing a permanent antibacterial acrylic bathroom board according to claim 1, characterized in that: In step three, the addition ratio of acrylic prepolymer, antibacterial agent slurry, multifunctional acrylate crosslinker, and low-temperature initiator is: 100 parts of the total amount of acrylic prepolymer (including the acrylic prepolymer in the preparation of the antibacterial agent slurry), 0.3-0.6 parts of antibacterial agent, 0.01-0.05 parts of multifunctional acrylate crosslinker, and 0.01-0.05 parts of low-temperature initiator. Mix and stir evenly, and vacuum to remove bubbles.

5. The method for preparing a permanent antibacterial acrylic bathroom board according to claim 2, characterized in that: The terminal hydroxyl acrylate is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxymethyl methacrylate.

6. The method for preparing a permanent antibacterial acrylic bathroom board according to claim 2, characterized in that: The terminal phosphate monomer is one or more of methacryloyloxyethyl ester, methacryloyloxyethyl ester, methacryloyloxyethyl ester, acryloyloxyethyl ester, acryloyloxyethyl ester, acryloyloxyethyl ester, methacryloyloxyethyl ester, diethyl acryloyloxyethyl ester, and diethyl acryloyloxyethyl ester.

7. The method for preparing a permanent antibacterial acrylic bathroom board according to claim 2, characterized in that: The high temperature initiator is any one of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), di(4-methylbenzoyl) peroxide, tri-pentyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate.

8. The method for preparing a permanent antibacterial acrylic bathroom board according to claim 3, characterized in that: The antibacterial agent is a silver ion antibacterial agent.

9. The method for preparing a permanent antibacterial acrylic bathroom board according to claim 4, characterized in that: The multifunctional acrylate crosslinking agent is any one of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, triisocyanuric acid triacrylate, and trimethylolpropane triacrylate.

10. The method for preparing a permanent antibacterial acrylic bathroom board according to claim 4, characterized in that: The low-temperature initiator is any one of azobisisoheptanenitrile, diisobutyryl peroxide, cumyl peroxyneodecanoate, and bis(3-methoxybutyl)peroxydicarbonate.

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