CN115972721A - Antibacterial acrylic sheet and preparation method and application thereof - Google Patents
Antibacterial acrylic sheet and preparation method and application thereof Download PDFInfo
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- CN115972721A CN115972721A CN202310053727.5A CN202310053727A CN115972721A CN 115972721 A CN115972721 A CN 115972721A CN 202310053727 A CN202310053727 A CN 202310053727A CN 115972721 A CN115972721 A CN 115972721A
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- antibacterial
- acrylic
- methyl methacrylate
- temperature initiator
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010410 layer Substances 0.000 claims abstract description 160
- 239000000178 monomer Substances 0.000 claims abstract description 43
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 36
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 22
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 68
- 239000003999 initiator Substances 0.000 claims description 68
- 239000000463 material Substances 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 239000003242 anti bacterial agent Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 21
- -1 alkyl glucoside Chemical class 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical group CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 5
- 229930182478 glucoside Natural products 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000013047 polymeric layer Substances 0.000 claims description 3
- 229950008882 polysorbate Drugs 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims 1
- 239000001023 inorganic pigment Substances 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000005336 cracking Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- HSOOIVBINKDISP-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CCC)OC(=O)C(C)=C HSOOIVBINKDISP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005399 allylmethacrylate group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 206010037833 rales Diseases 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RZTYEUCBTNJJIW-UHFFFAOYSA-K silver;zirconium(4+);phosphate Chemical group [Zr+4].[Ag+].[O-]P([O-])([O-])=O RZTYEUCBTNJJIW-UHFFFAOYSA-K 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003971 tillage Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to an antibacterial acrylic sheet and a preparation method and application thereof. The antibacterial acrylic sheet is characterized by comprising an upper layer and a lower layer, wherein the upper layer is an antibacterial acrylic layer, and the lower layer is an acrylic layer. According to the invention, titanium dioxide is added to the upper antibacterial acrylic layer, inorganic pigment titanium dioxide is not added to the lower acrylic layer, and toughening monomer and cross-linking agent are added to the upper layer, so that the white appearance and the plastic suction tensile property of the plate are ensured; the invention adopts the mode of the upper layer of the antibacterial acrylic layer and the lower layer of the acrylic layer to solve the problems of insufficient durability and low yield rate existing in the scheme of spraying the acrylic surface layer.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an antibacterial acrylic sheet and a preparation method and application thereof.
Background
The acrylic polymer is an important plastic polymer material which is developed earlier, has the characteristics of good transparency, chemical stability, weather resistance, hardness, easiness in dyeing, easiness in processing, strong light transmittance, high printing adhesion, attractive appearance, recoverability and the like, and is widely applied to various industries. The acrylic material is often applied to sanitary products, and because the environment is moist and closed, the surface of the acrylic sanitary product is easy to breed bacteria to influence human health in the using process. The existing acrylic sheet generally does not have an antibacterial function, and if the antibacterial function is to be realized, the antibacterial function is realized by surface treatment of an antibacterial coating or a mode of adding an antibacterial agent into an acrylic sheet body.
The surface treatment of the antibacterial coating has the problem of poor coating stability, and when the antibacterial coating is used on a bathtub, the coating is easy to fall off, bubble and the like due to frequent water soaking of the antibacterial coating on the surface, so that the stability is poor. The appearance uniformity of the antibacterial coating is difficult to ensure, and the bath tub has a plurality of curved surfaces and a large area, so that the defects of sagging, pollution and the like are easily caused during the surface treatment of the antibacterial coating, and the yield is low. The addition of the antibacterial agent into the acrylic sheet body has higher cost because of larger consumption of the required antibacterial agent. Meanwhile, the antibacterial agent is zirconium phosphate silver-loaded or glass silver-loaded powder which is an inorganic substance and is not added in a small amount, so that the influence of the addition of the antibacterial agent on the plastic suction tensile property of the plate is large, the plastic suction forming property of the bathtub can be influenced, the problems of cracking during plastic suction forming and poor adhesive force during post-treatment spraying of a glass fiber reinforced material exist, the yield is influenced, and the cost is further increased.
Therefore, it is very necessary to develop a new antibacterial acrylic sheet to solve the above problems.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an antibacterial acrylic sheet and a preparation method and application thereof.
In order to achieve the above purpose, one of the technical solutions of the present invention is: an antibacterial acrylic plate comprises an upper layer and a lower layer, wherein the upper layer is an antibacterial acrylic layer, and the lower layer is an acrylic layer.
In a preferred embodiment of the invention, the antibacterial acrylic layer material comprises methyl methacrylate, a high-temperature initiator, a release agent, a low-temperature initiator, a cross-linking agent, a toughening monomer, titanium dioxide and an antibacterial agent; the upper antibacterial acrylic layer material comprises, by weight, 90-95% of methyl methacrylate, 0.01-0.2% of a high-temperature initiator, 0.05-5% of a release agent, 0.01-0.2% of a low-temperature initiator, 0.5-3.0% of a cross-linking agent, 2-6% of a toughening monomer, 0.2-4% of titanium dioxide and 2-4% of an antibacterial agent.
In a preferred embodiment of the present invention, the lower acrylic material comprises methyl methacrylate, a high temperature initiator, a release agent, a low temperature initiator, a cross-linking agent and a toughening monomer; the lower acrylic material comprises 90wt% -99.5 wt% of methyl methacrylate, 0.01wt% -0.2 wt% of high-temperature initiator, 0.05wt% -0.5 wt% of release agent, 0.01wt% -0.2 wt% of low-temperature initiator, 0-2.0 wt% of cross-linking agent and 0-3.0 wt% of toughening monomer according to weight ratio.
Further, the high-temperature initiator comprises azobisisoheptonitrile, the low-temperature initiator comprises azobisisobutyronitrile, and the crosslinking agent comprises one of glycol dimethacrylate, butanediol dimethacrylate, allyl methacrylate and acrylamide; the release agent comprises one or more of nonionic surfactant, cationic surfactant and anionic surfactant; the toughening monomer is isooctyl methacrylate.
The toughening monomer is a necessary component on the upper antibacterial acrylic layer, and because the upper antibacterial powder and the inorganic pigment-titanium dioxide are added to ensure the white appearance and the antibacterial performance, the tensile property is poor, so the toughening monomer is added to ensure that the tensile property is unchanged; the lower acrylic layer is not added with any inorganic antibacterial agent and inorganic pigment-titanium dioxide, so that the tensile property of the lower acrylic layer is not influenced, a toughening monomer is not needed, and the tensile property can be further improved if a little toughening monomer is added; especially, when the thickness of the lower layer is thinner, some toughening monomers can be properly added, and if the thickness of the lower layer is thicker, the toughening monomers can not be added.
Still further, the nonionic surfactant comprises one or more of an alkyl glucoside, a fatty acid glyceride, a fatty acid sorbitan, and a polysorbate; the anionic surfactant comprises one or more of fatty acid salt, sodium alkyl benzene sulfonate and phosphate ester salt; the cationic surfactant comprises one or more of amine salt type, quaternary ammonium salt type, heterocyclic type and rale salt type.
In a preferred embodiment of the present invention, the thickness of the antibacterial acrylic layer is controlled to be 0.5-1.5 mm.
In a preferred embodiment of the present invention, the thickness of the pure acrylic layer is controlled to be 1.5-3.5 mm.
In order to achieve the above purpose, the second technical solution of the present invention is: an application of antibacterial acrylic plate in bathtub.
In a preferred embodiment of the invention, the front layer of the bathtub is an upper layer of the antibacterial acrylic plate, and the back layer of the bathtub is a lower layer of the antibacterial acrylic plate.
In order to achieve the above purpose, the third technical scheme of the invention is as follows: the preparation method of the antibacterial acrylic plate comprises the following steps:
s1: preparation of the lower acrylic layer semi-polymeric layer
(1) Adding a high-temperature initiator into methyl methacrylate, boiling the methyl methacrylate by heating, keeping the boiling state for 10-15 min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent and a toughening monomer into the methyl methacrylate prepolymer, and then stirring and mixing to obtain a mixture, wherein the stirring and mixing time is 15-30 min;
(3) Placing the obtained mixture in a vacuum environment for defoaming; placing the defoamed material in a prepared mould, and removing bubbles;
(4) Placing the material without bubbles and the mould in a water bath at 60 ℃ for water bath polymerization for 1-3 h to obtain a lower acrylic layer semi-polymerization layer; then taking out the upper die of the die for the next working procedure;
s2: preparing the raw material mixed solution of the upper antibacterial acrylic layer
(1) Adding a high-temperature initiator into methyl methacrylate, heating to reach the boiling point of the methyl methacrylate, keeping the boiling state for 15-20 min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent, titanium dioxide, an antibacterial agent and a toughening monomer into the methyl methacrylate prepolymer, and then stirring and mixing for 15-30 min to obtain a mixture;
(3) Placing the obtained mixture in a vacuum environment, and defoaming to obtain an upper-layer antibacterial acrylic layer raw material mixed solution;
s3: preparing antibacterial acrylic plate
(1) Placing the mixed solution of the raw materials of the upper antibacterial acrylic layer prepared in the step S2 on the semi-polymerized layer of the lower acrylic layer prepared in the step S1, installing an upper die and removing bubbles;
(2) Placing the mold filled with the upper antibacterial acrylic layer raw material mixed solution and the lower acrylic layer semi-polymerization layer in a water bath at 50-70 ℃ for water bath polymerization for 2-6 h, and then placing the mold at 100-120 ℃ for polymerization for 2-4 h; and cooling and demoulding to obtain the antibacterial acrylic sheet.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, titanium dioxide is added to the upper antibacterial acrylic layer, inorganic pigment titanium dioxide is not added to the lower acrylic layer, and toughening monomer and cross-linking agent are added to the upper layer, so that white appearance and plastic uptake tensile property of the plate are ensured.
2. The invention adopts the mode of the upper antibacterial acrylic layer and the lower acrylic layer to solve the problems of insufficient durability and low yield in the scheme of spraying the acrylic surface layer.
3. The invention adopts the method that the antibacterial agent and the inorganic pigment are not added at the lower layer, but only added at the upper layer, thereby solving the problems of high cost, easy cracking and low yield rate existing in the process of adding the antibacterial agent and the inorganic pigment.
4. According to the invention, the antibacterial agent and the inorganic pigment are not added in the lower acrylic layer, so that the plasticity of the lower acrylic layer is improved, namely the elongation at break is improved, the processability is improved, and the problem of plate cracking in the plastic suction process is reduced; because the upper layer of the antibacterial acrylic layer is added with the inorganic pigment, the appearance is not influenced, and on the other hand, the antibacterial performance is not influenced because the antibacterial agent is added in the upper layer of the antibacterial acrylic layer.
5. According to the invention, the inorganic pigment and the inorganic antibacterial agent are added into the upper antibacterial acrylic layer, and the toughening monomer isooctyl methacrylate is also added, so that the antibacterial property and the appearance are ensured, and the elongation at break, namely the plastic uptake property, is also ensured.
6. The lower acrylic layer is in a semi-polymerization state and is not completely polymerized through technological parameter control in the forming process, and then the liquid material of the upper antibacterial layer is cast on the lower acrylic layer and is polymerized together, so that the integrity of the upper antibacterial acrylic layer and the lower acrylic layer is ensured, namely, the phenomenon of layering is avoided in the plastic suction process.
Detailed Description
The invention is further explained below with reference to specific examples.
An antibacterial acrylic sheet comprises an upper layer and a lower layer, wherein the upper layer is an antibacterial acrylic layer, and the lower layer is an acrylic layer.
The upper layer of antibacterial acrylic layer material comprises methyl methacrylate, a high-temperature initiator, a release agent, a low-temperature initiator, a cross-linking agent, a toughening monomer, titanium dioxide and an antibacterial agent; the upper layer antibacterial acrylic material comprises, by weight, 90-95% of methyl methacrylate, 0.01-0.2% of a high-temperature initiator, 0.05-0.5% of a release agent, 0.01-0.2% of a low-temperature initiator, 0.5-3.0% of a cross-linking agent, 0.2-4% of titanium dioxide, 2-4% of an antibacterial agent and 2-6% of a toughening monomer.
The lower acrylic material comprises methyl methacrylate, a high-temperature initiator, a release agent, a low-temperature initiator, a cross-linking agent and a toughening monomer; the lower acrylic material comprises 90wt% -99.5 wt% of methyl methacrylate, 0.01wt% -0.2 wt% of high-temperature initiator, 0.05wt% -0.5 wt% of release agent, 0.01wt% -0.2 wt% of low-temperature initiator, 0-2.0 wt% of cross-linking agent and 0-3 wt% of toughening monomer according to weight ratio.
The high-temperature initiator comprises azobisisoheptonitrile, the low-temperature initiator comprises azobisisobutyronitrile, and the crosslinking agent comprises one of ethylene glycol dimethacrylate, butanediol dimethacrylate and allyl methacrylate; the release agent comprises one or more of nonionic surfactant, cationic surfactant and anionic surfactant.
The non-ionic surfactant comprises one or more of alkyl glucoside, fatty glyceride, sorbitan fatty acid and polysorbate; the anionic surfactant comprises one or more of fatty acid salt, sodium alkyl benzene sulfonate and phosphate ester salt; the cationic surfactant comprises one or more of amine salt type, quaternary ammonium salt type, heterocyclic type and ralfate type. The toughening monomer is isooctyl methacrylate.
The antibacterial agent is silver-loaded zirconium phosphate or silver-loaded glass.
The thickness of the antibacterial acrylic layer is controlled to be 0.5-1.5 mm; the thickness of the acrylic layer is controlled to be 1.5-3.5 mm.
An application of antibacterial acrylic plate in bathtub.
The front layer of the bathtub is the upper layer of the antibacterial acrylic plate, and the back layer of the bathtub is the lower layer of the antibacterial acrylic plate.
A preparation method of an antibacterial acrylic plate comprises the following steps:
s1: preparation of the lower acrylic layer semi-polymeric layer
(1) Adding a high-temperature initiator into methyl methacrylate, boiling the methyl methacrylate by heating, keeping the boiling state for 10-15 min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent and a toughening monomer into the methyl methacrylate prepolymer, and then stirring and mixing for 15-30 min to obtain a mixture;
(3) Placing the mixture in vacuum for defoaming, then placing the mixture in a prepared mould in advance, and removing bubbles;
(4) Placing the material with the bubbles removed and a mould in a water bath at 50-70 ℃ for polymerization for 1-3 h to obtain a lower acrylic layer semi-polymerization layer;
s2: preparing the raw material mixed solution of the upper antibacterial acrylic layer
(1) Adding a high-temperature initiator into methyl methacrylate, heating to keep the methyl methacrylate in a boiling state for 15-20 min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent, titanium dioxide, an antibacterial agent and a toughening monomer into the methyl methacrylate prepolymer, and then stirring and mixing for 15-30 min to obtain a mixture;
(3) Placing the mixture in vacuum for defoaming to obtain an upper antibacterial acrylic layer raw material mixed solution;
s3: preparing antibacterial acrylic plate
(1) Pouring the mixed solution of the raw materials of the upper antibacterial acrylic layer prepared in the step S2 on the semi-polymerized layer of the lower acrylic layer prepared in the step S1, installing an upper die and removing bubbles;
(2) Placing the mould filled with the raw material mixed solution of the upper antibacterial acrylic layer and the semi-polymerized layer of the lower acrylic layer in a water bath at 50-70 ℃ for polymerization for 2-6 h, and then polymerizing for 2-4 h at 120-140 ℃; and cooling and demoulding to obtain the antibacterial acrylic sheet.
The purity of the methyl methacrylate used in the following examples is not less than 99.9%, and the methyl methacrylate is produced by Shanghai Caoxin chemical Co., ltd;
the high-temperature initiator is azobisisoheptonitrile, which is produced by one-ploughing chemical industry, inc., changzhou city; the release agent is alkyl glucoside, and the type is as follows: 0810, western land production in Guangzhou city; the low-temperature initiator is azodiisobutyronitrile produced by one-tillage chemical company Limited in Changzhou city; the cross-linking agent is allyl methacrylate aladine reagent net; titanium dioxide is 902+ specification, kemu brand; the antibacterial agent is purchased from Jinda nanometer science and technology (Xiamen) Co Ltd, is zirconium phosphate silver-carrying, and is a JDGKP-003H4 toughening monomer which is isooctyl methacrylate, and the content: more than 99.5 percent, produced by Shandong Haoyao new material Co.
Example 1
An antibacterial acrylic sheet comprises an upper antibacterial acrylic layer of 1.0 mm and a lower pure acrylic layer of 2.0 mm.
The upper layer antibacterial acrylic layer material comprises: 90wt% of methyl methacrylate, 0.15wt% of high-temperature initiator, 0.1wt% of release agent, 0.15wt% of low-temperature initiator, 0.5wt% of cross-linking agent, 1.1wt% of titanium dioxide, 2.0wt% of antibacterial agent and 6.0wt% of toughening monomer.
The inferior floor ya keli layer material is constituteed and is included: 97.8wt% of methyl methacrylate, 0.1wt% of high-temperature initiator, 0.05wt% of release agent, 0.05wt% of low-temperature initiator, 2.0wt% of cross-linking agent and 0wt% of toughening monomer.
The antibacterial acrylic layer is prepared according to the following steps:
s1: preparing the lower acrylic layer
(1) Adding a high-temperature initiator into methyl methacrylate, heating to boil the methyl methacrylate, keeping the boiling state for 15min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent and a toughening monomer into the methyl methacrylate prepolymer, and then stirring and mixing for 20min to obtain a mixture;
(3) Placing the obtained mixture in a vacuum environment for defoaming; placing the defoamed material in a prepared glass mold with the thickness of 2.0mm, and removing bubbles;
(4) Polymerizing the defoamed material, and demolding to obtain a lower pure acrylic layer with the thickness of 2.0 mm;
s2: preparing an upper antibacterial acrylic layer material
(1) Adding a high-temperature initiator into methyl methacrylate, heating to reach the boiling point of the methyl methacrylate, keeping the boiling state for 20min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent, titanium dioxide, an antibacterial agent and a toughening monomer into a methyl methacrylate prepolymer, and then stirring and mixing to obtain a mixture, wherein the stirring and mixing time is 25min;
(3) Placing the obtained mixture in a vacuum environment, and defoaming to obtain a lower-layer antibacterial acrylic layer material;
s3: preparing antibacterial acrylic sheet
(1) Performing plasma treatment on the upper surface of the pure acrylic layer prepared in the step S1;
(2) Placing the 2.0mm pure acrylic layer treated by the plasma in a glass mould with the thickness of 3.0 mm;
(3) Injecting the lower-layer antibacterial acrylic layer material obtained after the deaeration in the step S2 into the mold, and removing bubbles;
(4) Polymerizing the defoamed materials, and demolding to obtain the antibacterial acrylic sheet.
Example 2
An antibacterial acrylic sheet comprises an upper antibacterial acrylic layer of 0.5 mm and a lower pure acrylic layer of 3.0 mm.
The upper layer antibacterial acrylic layer material comprises: 92wt% of methyl methacrylate, 0.05wt% of high-temperature initiator, 0.05wt% of release agent, 0.05wt% of low-temperature initiator, 1wt% of cross-linking agent, 3.5wt% of titanium dioxide, 0.35wt% of antibacterial agent and 3wt% of toughening monomer.
The lower acrylic layer material comprises: 98.7wt% of methyl methacrylate, 0.05wt% of high-temperature initiator, 0.15wt% of release agent, 0.1wt% of low-temperature initiator, 0.5wt% of cross-linking agent and 0.5wt% of toughening monomer.
The antibacterial acrylic layer is prepared according to the following steps:
s1: preparing a lower acrylic layer
(1) Adding a high-temperature initiator into methyl methacrylate, boiling the methyl methacrylate by heating, keeping the boiling state for 10min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent and a toughening monomer into a methyl methacrylate prepolymer, and then stirring and mixing for 15min to obtain a mixture;
(3) Placing the obtained mixture in a vacuum environment for defoaming; placing the defoamed material in a prepared glass mold with the thickness of 3.0mm, and removing bubbles;
(4) Polymerizing the defoamed material, and demolding to obtain a lower pure acrylic layer with the thickness of 3.0 mm;
s2: preparing an upper antibacterial acrylic layer material
(1) Adding a high-temperature initiator into methyl methacrylate, heating to reach the boiling point of the methyl methacrylate, keeping the boiling state for 15min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent, titanium dioxide, an antibacterial agent and a toughening monomer into a methyl methacrylate prepolymer, and then stirring and mixing to obtain a mixture, wherein the stirring and mixing time is 30min;
(3) Placing the obtained mixture in a vacuum environment, and defoaming to obtain a lower-layer antibacterial acrylic layer material;
s3: preparing antibacterial acrylic sheet
(1) Performing plasma treatment on the upper surface of the pure acrylic layer prepared in the step S1;
(2) Placing the 3.0mm pure acrylic layer treated by the plasma in a glass mould with the thickness of 3.5 mm;
(3) Injecting the lower-layer antibacterial acrylic layer material obtained after defoaming in the step S2 into the mold, and removing bubbles;
(4) Polymerizing the defoamed materials, and demolding to obtain the antibacterial acrylic sheet.
Example 3
An antibacterial acrylic sheet comprises an upper antibacterial acrylic layer of 1.5mm and a lower pure acrylic layer of 1.5 mm.
The upper layer antibacterial acrylic layer material comprises: 93wt% of methyl methacrylate, 0.05wt% of high-temperature initiator, 0.05wt% of release agent, 0.05wt% of low-temperature initiator, 1.5wt% of cross-linking agent, 2wt% of titanium dioxide, 0.35wt% of antibacterial agent and 3wt% of toughening monomer.
The inferior floor ya keli layer material is constituteed and is included: 96.2wt% of methyl methacrylate, 0.15wt% of high-temperature initiator, 0.45wt% of release agent, 0.2wt% of low-temperature initiator, 0wt% of cross-linking agent and 3wt% of toughening monomer.
The antibacterial acrylic layer is prepared according to the following steps:
s1: preparing the lower acrylic layer
(1) Adding a high-temperature initiator into methyl methacrylate, boiling the methyl methacrylate by heating, keeping the boiling state for 13min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent and a toughening monomer into the methyl methacrylate prepolymer, and then stirring and mixing for 30min to obtain a mixture;
(3) Placing the obtained mixture in a vacuum environment for defoaming; placing the defoamed material in a prepared glass mold with the thickness of 1.5mm, and removing bubbles;
(4) Polymerizing the defoamed materials, and demolding to obtain a lower pure acrylic layer with the thickness of 1.5 mm;
s2: preparing an upper antibacterial acrylic layer material
(1) Adding a high-temperature initiator into methyl methacrylate, heating to reach the boiling point of the methyl methacrylate, keeping the boiling state for 18min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent, titanium dioxide, an antibacterial agent and a toughening monomer into the methyl methacrylate prepolymer, and then stirring and mixing for 18min to obtain a mixture;
(3) Placing the obtained mixture in a vacuum environment, and defoaming to obtain a lower-layer antibacterial acrylic layer material;
s3: preparing antibacterial acrylic sheet
(1) Performing plasma treatment on the upper surface of the pure acrylic layer prepared in the step S1;
(2) Placing the 1.5mm pure acrylic layer treated by the plasma in a glass mould with the thickness of 3.0 mm;
(3) Injecting the lower-layer antibacterial acrylic layer material obtained after the deaeration in the step S2 into the mold, and removing bubbles;
(4) Polymerizing the defoamed materials, and demolding to obtain the antibacterial acrylic sheet.
The antibacterial acrylic sheet prepared in examples 1 to 3, and the sheet and the coated antibacterial sheet with the antibacterial agent added to the whole body were tested, wherein the antibacterial property and the antibacterial durability were tested according to the national standard technical specification for antibacterial performance of the antibacterial plastic tube for construction JCT 939-2004, and the boiling resistance was tested by heating with hot water at 65 ℃ for 100 hours to observe the appearance; the processability is tested by observing whether the plastic suction molding has bad phenomena such as cracking, layering and the like, and the following test results are obtained:
the above embodiments are merely preferred embodiments of the present invention, which are intended to illustrate the principles and functions of the present invention, and not to limit the present invention. It should be noted that modifications to the above-described embodiments can be made by persons skilled in the art without departing from the spirit and scope of the invention, and such modifications should also be considered as within the scope of the invention.
Claims (10)
1. The antibacterial acrylic sheet is characterized by comprising an upper layer and a lower layer, wherein the upper layer is an antibacterial acrylic layer, and the lower layer is an acrylic layer.
2. The antibacterial acrylic sheet according to claim 1, wherein the upper antibacterial acrylic layer comprises methyl methacrylate, a high-temperature initiator, a release agent, a low-temperature initiator, a cross-linking agent, a toughening monomer, titanium dioxide and an antibacterial agent; the material of the upper antibacterial acrylic layer comprises 90-95 wt% of methyl methacrylate, 0.01-0.2 wt% of high-temperature initiator, 0.05-0.5 wt% of release agent, 0.01-0.2 wt% of low-temperature initiator, 0.5-3.0 wt% of cross-linking agent, 2-6 wt% of toughening monomer, 0.2-4 wt% of titanium dioxide and 2-4 wt% of antibacterial agent according to weight ratio.
3. The antibacterial acrylic sheet according to claim 2, wherein the antibacterial agent is silver-supported zirconium phosphate or silver-supported glass.
4. The antibacterial acrylic sheet according to claim 1, wherein the lower acrylic material comprises methyl methacrylate, a high temperature initiator, a release agent, a low temperature initiator, a cross-linking agent and a toughening monomer; the material of the lower acrylic layer comprises 90wt% -99.5 wt% of methyl methacrylate, 0.01wt% -0.2 wt% of high-temperature initiator, 0.05wt% -0.5 wt% of release agent, 0.01wt% -0.2 wt% of low-temperature initiator, 0-2.0 wt% of cross-linking agent and 0-3 wt% of toughening monomer according to weight ratio.
5. The antibacterial acrylic sheet according to any one of claims 1 or 4, wherein the high temperature initiator comprises azobisisoheptonitrile, the low temperature initiator comprises azobisisobutyronitrile, and the crosslinking agent comprises one or more of ethylene glycol dimethacrylate, butylene glycol dimethacrylate, allyl methacrylate, acrylamide; the release agent comprises one or more of nonionic surfactant, cationic surfactant and anionic surfactant; the toughening monomer is isooctyl methacrylate.
6. The antibacterial acrylic sheet according to claim 5, wherein the nonionic surfactant comprises one or more of alkyl glucoside, fatty acid glyceride, sorbitan fatty acid, and polysorbate; the anionic surfactant comprises one or more of fatty acid salt, sodium alkyl benzene sulfonate and phosphate ester salt; the cationic surfactant comprises one or more of amine salt type, quaternary ammonium salt type, heterocyclic type and ralfate type.
7. The antibacterial acrylic sheet according to claim 1, wherein the thickness of the antibacterial acrylic layer is controlled to be 0.5-1.5 mm; the thickness of the acrylic layer is controlled to be 1.5-3.5 mm.
8. Use of an antibacterial acrylic sheet as claimed in any one of claims 1 to 7 in a bath tub.
9. The use according to claim 8 wherein the front layer of the bath is an upper layer of antibacterial acrylic sheet and the back layer of the bath is a lower layer of antibacterial acrylic sheet.
10. A method for preparing the antibacterial acrylic sheet as claimed in any one of claims 1 to 7, comprising the steps of:
s1: preparation of the lower acrylic layer semi-polymeric layer
(1) Adding a high-temperature initiator into the methyl methacrylate, heating to boil the methyl methacrylate, keeping the boiling state for 10-15 min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
(2) Adding a release agent, a low-temperature initiator, a cross-linking agent and a toughening monomer into the methyl methacrylate prepolymer, and then stirring and mixing for 15-30 min to obtain a mixture;
(3) Placing the mixture in vacuum for defoaming, then placing the mixture in a prepared mould in advance, and removing bubbles;
(4) Placing the material with the bubbles removed and the mould in a water bath at 50-70 ℃ for polymerization for 1-3 h to obtain a lower acrylic layer semi-polymerization layer;
s2: preparing a raw material mixed solution of an upper antibacterial acrylic layer
(1) Adding a high-temperature initiator into methyl methacrylate, heating to keep the methyl methacrylate in a boiling state for 15-20 min, and naturally cooling to normal temperature to obtain a methyl methacrylate prepolymer;
adding a release agent, a low-temperature initiator, a cross-linking agent, titanium dioxide, an antibacterial agent and a toughening monomer into the methyl methacrylate prepolymer, and then stirring and mixing for 15-30 min to obtain a mixture;
(2) Placing the mixture in vacuum for defoaming to obtain an upper antibacterial acrylic layer raw material mixed solution;
s3: preparing antibacterial acrylic plate
(1) Pouring the raw material mixed solution of the upper antibacterial acrylic layer prepared in the step S2 into the lower acrylic prepared in the step S1
Installing an upper die on the force layer semi-polymerization layer and removing bubbles;
(2) Placing the mould filled with the raw material mixed solution of the upper antibacterial acrylic layer and the semi-polymerized layer of the lower acrylic layer in a water bath at 50-70 ℃ for polymerization for 2-6 h, and then polymerizing for 2-4 h at 100-120 ℃; and cooling and demoulding to obtain the antibacterial acrylic sheet.
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