CN115785517B - Antibacterial foaming cushion and preparation method thereof - Google Patents
Antibacterial foaming cushion and preparation method thereof Download PDFInfo
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- CN115785517B CN115785517B CN202210372309.8A CN202210372309A CN115785517B CN 115785517 B CN115785517 B CN 115785517B CN 202210372309 A CN202210372309 A CN 202210372309A CN 115785517 B CN115785517 B CN 115785517B
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Abstract
The invention discloses an antibacterial foaming cushion, which comprises a basal layer and a surface functional layer compounded on the basal layer; the surface functional layer is composed of the following raw materials in parts by weight: 80 to 100 parts of PVC paste resin, 20 to 30 parts of acrylate resin, 1 to 3 parts of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 3 to 8 parts of plasticizer, 5 to 15 parts of composite antibacterial agent, 1.5 to 2.5 parts of pigment, 2 to 5 parts of sodium dodecyl polyoxyethylene ether sulfate, 0.5 to 3.5 parts of heat stabilizer and 15 to 30 parts of solvent. The foaming cushion disclosed by the invention not only has excellent heat stability and rebound resilience, but also has excellent antibacterial property, and can ensure the safety, reliability and comfort of use under different outdoor complex environments.
Description
Technical Field
The invention relates to the technical field of foaming plastics, in particular to an antibacterial foaming cushion and a preparation method thereof.
Background
With the improvement of society, the living standard of people is improved, and outdoor life is pursued by people. The outdoor products are increasingly demanded, which puts higher demands on the outdoor product industry, and the outdoor products are also required to be continuously improved to adapt to new living demands.
The PVC cushion has good chemical stability and strong tensile, bending, compression and impact resistance. However, the outdoor environment is complex, the rebound resilience and the thermal stability of the existing outdoor PVC cushion are poor, and the overall comfort is poor after long-term use. The rebound resilience is poor, and the service life of the cushion is further reduced; in hot summer, the cushion is easy to generate certain viscosity under the action of high temperature, and the comfort is reduced. In addition, the performance of PVC mat reduces and stacks complicated outdoor environment, and the mat easily breeds the bacterium, reduces the life of PVC mat, has improved health and safety risk.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention provides an antibacterial foaming cushion, which solves the problems that the prior foaming cushion cannot be taken into consideration in terms of heat stability, rebound resilience, antibacterial property and the like, and the safety, reliability and comfort of use under different outdoor complex environments are difficult to ensure.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an antimicrobial foam mat comprising a substrate layer and a surface functional layer compounded on the substrate layer; the surface functional layer is composed of the following raw materials in parts by weight: 80 to 100 parts of PVC paste resin, 20 to 30 parts of acrylate resin, 1 to 3 parts of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 3 to 8 parts of plasticizer, 5 to 15 parts of composite antibacterial agent, 1.5 to 2.5 parts of pigment, 2 to 5 parts of sodium dodecyl polyoxyethylene ether sulfate, 0.5 to 3.5 parts of heat stabilizer and 15 to 30 parts of solvent.
Preferably, the acrylate resin is at least one of ethyl acrylate, butyl acrylate, methacrylate, n-butyl methacrylate, methyl methacrylate and hydroxyethyl methacrylate. Further, the resin polymer is obtained by copolymerizing at least one of ethyl acrylate, butyl acrylate, methacrylate, n-butyl methacrylate, methyl methacrylate and hydroxyethyl methacrylate as a monomer.
Preferably, the plasticizer is at least one of dioctyl phthalate, dibutyl phthalate, dinonyl phthalate, butyl benzyl phthalate.
Preferably, the heat stabilizer is at least one of zinc stearate, calcium stearate and di-n-butyltin dilaurate.
Preferably, the composite antibacterial agent is nano metal particles coated by pyridinium derivatives. Preferably, the nano metal particles are silver or zinc. The composite antibacterial agent of the application exerts the antibacterial effect of the pyridinium derivative and the nano metal particles in a synergistic way, and enables the nano metal particles to be uniformly dispersed in the foaming pad in a coating treatment mode, so that the agglomeration caused by the nano effect of the metal particles is prevented, the uniform dispersion is difficult, and the overall performance of the foaming pad is reduced.
Preferably, the substrate layer is prepared from raw materials compounded by PVC powder, modified waste rubber powder, a plasticizer, a foaming agent, an inorganic filler, an antibacterial liquid, a heat stabilizer and a solvent.
Preferably, the modification method of the modified waste rubber powder comprises the following steps: 100 parts of waste rubber powder and 10-30 parts of PVC powder are weighed according to parts by weight and added into an internal mixer, then methacrylic acid ester which is 5-10% of the mass of the waste rubber powder and an initiator which is 0.1-0.5% of the mass of the waste rubber powder are added, and after swelling and mixing uniformly, the modified waste rubber powder is obtained through vulcanization and interface reaction at the vulcanization temperature of 100-200 ℃. Preferably, the waste rubber powder is at least one selected from NBR nitrile rubber, ABS resin and SBR styrene butadiene rubber.
Preferably, the foaming agent is prepared by compounding azodicarbonamide or N, N-dinitroso pentamethylene tetramine with sodium bicarbonate.
Preferably, the antibacterial liquid is prepared by compounding pyridinium ionic liquid shown in a structural formula I with tetrahydrofuran,
wherein the ratio of m to n is 2:3.
The compound pyridinium ionic liquid is obtained by carrying out substitution reaction on 4-amyl-pyridine and 2-chloroethyl methacrylate and then carrying out polymerization reaction on the compound pyridinium ionic liquid and acryloyloxyethyl trimethyl ammonium chloride. The pyridinium ionic liquid not only promotes the compatibility of inorganic components and organic components in raw materials, so that the inorganic components and the organic components are uniformly dispersed, the overall performance of the foaming cushion is improved, and the problem of local cracking is effectively reduced; the heat stability and the flame retardant property of the foaming cushion are improved due to the plurality of pyridinium structures; in addition, the plurality of quaternary ammonium salt functional groups carried by the pyridinium ionic liquid improve the antibacterial property of the polyvinyl chloride foaming pad, and the copolymer with the acrylate structure promotes the easy processing property of the foaming pad.
Another aspect of the present invention is to provide a method for preparing the antibacterial foaming pad as described above, the method comprising the steps of:
step S1: foaming and molding a substrate layer raw material compounded by 50-100 parts of PVC powder, 8-16 parts of modified waste rubber powder, 12-20 parts of plasticizer, 2-6 parts of foaming agent, 2-6 parts of inorganic filler, 0.5-3.5 parts of heat stabilizer and 15-30 parts of solvent in a mold to obtain a substrate layer;
step S2: preparing an antibacterial solution by combining pyridinium ionic liquid and tetrahydrofuran, and soaking the substrate layer obtained in the step S1 in the antibacterial solution for 10-60 min;
step S3: mixing 80-100 parts of PVC paste resin, 20-30 parts of acrylate resin, 1-3 parts of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 3-8 parts of plasticizer, 5-15 parts of composite antibacterial agent, 1.5-2.5 parts of pigment, 2-5 parts of sodium dodecyl polyoxyethylene ether sulfate, 0.5-3.5 parts of heat stabilizer and 15-30 parts of solvent into mixed emulsion, coating the mixed emulsion on the substrate layer treated in the step S2 in a spraying manner, and curing to obtain the antibacterial foaming pad compounded with the surface functional layer.
The invention has the beneficial effects that:
compared with the existing antibacterial foaming cushion, the antibacterial foaming cushion has excellent heat stability and rebound resilience, has excellent antibacterial property, and can ensure the safety, reliability and comfort of use under different outdoor complex environments.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
The antibacterial foaming cushion comprises a basal layer and a surface functional layer compounded on the basal layer; the surface functional layer is composed of the following raw materials in parts by weight: 80 parts of PVC paste resin, 20 parts of methacrylate resin, 1 part of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 3 parts of dioctyl phthalate, 5 parts of composite antibacterial agent, 1.5 parts of phthalocyanine green, 2 parts of sodium dodecyl polyoxyethylene ether sulfate, 0.5 part of di-n-butyltin dilaurate and 15 parts of acetone.
The substrate layer is prepared from raw materials compounded by PVC powder, modified waste rubber powder, dioctyl phthalate, a foaming agent, carbon black, an antibacterial liquid, di-n-butyltin dilaurate and ethylene glycol phenyl ether. The foaming agent comprises the following components in percentage by mass: 2 with sodium bicarbonate.
The preparation method of the antibacterial foaming pad comprises the following steps:
step S1: foaming and molding a substrate layer raw material compounded by 50 parts of PVC powder, 8 parts of modified waste rubber powder, 12 parts of dioctyl phthalate, 2 parts of foaming agent, 2 parts of carbon black, 0.5 part of di-n-butyltin dilaurate and 15 parts of ethylene glycol phenyl ether in a mold to obtain a substrate layer;
step S2: the mass ratio is 1:10, compounding a pyridinium ionic liquid and tetrahydrofuran to form an antibacterial liquid, and soaking the substrate layer obtained in the step S1 in the antibacterial liquid for 30min;
step S3: the antibacterial foaming cushion compounded with the surface functional layer is prepared by mixing 80 parts of PVC paste resin, 20 parts of methacrylate resin, 1 part of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 3 parts of dioctyl phthalate, 5 parts of composite antibacterial agent, 1.5 parts of phthalocyanine green, 2 parts of sodium dodecyl polyoxyethylene ether sulfate, 0.5 part of di-n-butyltin dilaurate and 15 parts of acetone into mixed emulsion, coating the mixed emulsion on a substrate layer treated in the step S2 in a spraying mode, and curing.
The modification method of the modified waste rubber powder comprises the following steps: 100 parts of waste rubber powder and 20 parts of PVC powder are weighed according to parts by weight and added into an internal mixer, and then methacrylic acid ester which is equivalent to 5% of the mass of the waste rubber powder and an initiator which is equivalent to 0.1% of the mass of the waste rubber powder are added, and after swelling and mixing uniformly, the modified waste rubber powder is obtained through vulcanization and interfacial reaction at the vulcanization temperature of 200 ℃. The waste rubber powder is selected from SBR styrene butadiene rubber.
The specific preparation method of the pyridinium ionic liquid (the chemical formula is shown as a structural formula I) comprises the following steps: dissolving 0.1mol of 4-amyl-pyridine and 0.1mol of 2-chloroethyl methacrylate in 1L of tetrahydrofuran solution, heating and refluxing for 36 hours under stirring, and filtering to obtain an acrylate substituted pyridine derivative; 0.2mol of acrylate substituted pyridine derivative and 0.3mol of acryloyloxyethyl trimethyl ammonium chloride are dissolved in 1L of ethanol solution, and 0.01g of azodiisobutyronitrile is added as a free radical initiator for copolymerization to obtain a pyridinium ionic liquid shown in a structural formula I.
The chemical structure is characterized as follows:
h1NMR (DMSO-d 6): delta 0.81-1.03 (12H), 1.09-1.35 (17H), 1.51-1.85 (12H), 1.96-2.08 (2H), 2.40-2.64 (6H), 2.79-2.90 (27H), 3.29-3.41 (6H), 4.38-4.56 (10H), 4.70-4.82 (4H), 7.53-7.66 (3H), 8.17 (2H), 8.67-8.80 (3H). It can thus be stated that the acrylate-substituted pyridine derivative is copolymerized with acryloyloxyethyl trimethylammonium chloride substantially in a 2:3 ratio.
The specific preparation method of the composite antibacterial agent comprises the following steps: dissolving 0.1mol of 4-amyl-pyridine and 0.1mol of 2-chloroethyl methacrylate in 1L of tetrahydrofuran solution, heating and refluxing for 36 hours under stirring, and filtering to obtain an acrylate substituted pyridine derivative; taking 0.1mol of acrylate substituted pyridine derivative, adding 5g of nano metal silver particles and 50g of glycerol, and stirring and mixing uniformly by ultrasonic waves; then 0.4mol of acryloyloxyethyl trimethyl ammonium chloride is added as a functional auxiliary agent, 0.4mol of isoprene is added as a chain extender, and 0.3g of azodiisobutyronitrile is added as a free radical initiator to carry out in-situ copolymerization reaction on the surfaces of nano metal silver particles, so as to obtain the nano metal silver particles coated by the pyridinium derivative.
Example 2
The antibacterial foaming cushion comprises a basal layer and a surface functional layer compounded on the basal layer; the surface functional layer is composed of the following raw materials in parts by weight: 90 parts of PVC paste resin, 25 parts of methacrylate resin, 2 parts of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 5 parts of dibutyl phthalate, 10 parts of composite antibacterial agent, 2 parts of phthalocyanine blue, 3 parts of sodium dodecyl polyoxyethylene ether sulfate, 1.5 parts of zinc stearate and 20 parts of acetone.
The substrate layer is prepared from raw materials compounded by PVC powder, modified waste rubber powder, dioctyl phthalate, dibutyl phthalate, a foaming agent, carbon black, antibacterial liquid, zinc stearate and ethylene glycol phenyl ether. The foaming agent comprises the following components in percentage by mass: 2 with sodium bicarbonate.
The preparation method of the antibacterial foaming pad comprises the following steps:
step S1: foaming and molding a substrate layer raw material compounded by 70 parts of PVC powder, 12 parts of modified waste rubber powder, 18 parts of dioctyl phthalate, dibutyl phthalate, 4 parts of foaming agent, 5 parts of carbon black, 2.5 parts of zinc stearate and 20 parts of ethylene glycol phenyl ether in a mold to obtain a substrate layer;
step S2: the mass ratio is 1:10, compounding a pyridinium ionic liquid and tetrahydrofuran to form an antibacterial liquid, and soaking the substrate layer obtained in the step S1 in the antibacterial liquid for 30min;
step S3: the antibacterial foaming cushion with the surface functional layer is prepared by mixing raw materials compounded by 90 parts of PVC paste resin, 25 parts of methacrylate resin, 2 parts of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 5 parts of dibutyl phthalate, 10 parts of composite antibacterial agent, 2 parts of phthalocyanine blue, 3 parts of sodium dodecyl polyoxyethylene ether sulfate, 1.5 parts of zinc stearate and 20 parts of acetone into a mixed emulsion, coating the mixed emulsion on a substrate layer treated in the step S2 in a spraying manner, and curing the mixed emulsion.
The modification method of the modified waste rubber powder in this example is the same as in example 1, and the specific preparation method of the pyridinium ionic liquid and the composite antibacterial agent is the same as in example 1.
Example 3
The antibacterial foaming cushion comprises a basal layer and a surface functional layer compounded on the basal layer; the surface functional layer is composed of the following raw materials in parts by weight: 100 parts of PVC paste resin, 30 parts of methacrylate resin, 3 parts of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 8 parts of dioctyl phthalate, 15 parts of composite antibacterial agent, 2.5 parts of titanium dioxide, 5 parts of sodium dodecyl polyoxyethylene ether sulfate, 3.5 parts of calcium stearate and 30 parts of acetone.
The substrate layer is prepared from raw materials compounded by PVC powder, modified waste rubber powder, dioctyl phthalate, dibutyl phthalate, a foaming agent, carbon black, an antibacterial liquid, calcium stearate and ethylene glycol phenyl ether. The foaming agent comprises the following components in percentage by mass: 2 with sodium bicarbonate.
The preparation method of the antibacterial foaming pad comprises the following steps:
step S1: foaming and molding a substrate layer raw material compounded by 100 parts of PVC powder, 16 parts of modified waste rubber powder, 20 parts of dioctyl phthalate, 6 parts of foaming agent, 6 parts of carbon black, 3.5 parts of calcium stearate and 30 parts of ethylene glycol phenyl ether in a mold to obtain a substrate layer;
step S2: the mass ratio is 1:10, compounding a pyridinium ionic liquid and tetrahydrofuran to form an antibacterial liquid, and soaking the substrate layer obtained in the step S1 in the antibacterial liquid for 30min;
step S3: the antibacterial foaming cushion with the surface functional layer is prepared by mixing 100 parts of PVC paste resin, 30 parts of methacrylate resin, 3 parts of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 8 parts of dioctyl phthalate, 15 parts of composite antibacterial agent, 2.5 parts of titanium dioxide, 5 parts of sodium dodecyl polyoxyethylene ether sulfate, 3.5 parts of calcium stearate and 30 parts of acetone to form a mixed emulsion, coating the mixed emulsion on a substrate layer treated in the step S2 in a spraying manner, and curing the mixed emulsion.
The modification method of the modified waste rubber powder in this example is the same as in example 1, and the specific preparation method of the pyridinium ionic liquid and the composite antibacterial agent is the same as in example 1.
Comparative example 1
The antibacterial foamed mat of this comparative example was basically the same in the raw material composition as in example 1 except that the raw material of the base layer of the antibacterial foamed mat of this comparative example did not contain modified waste rubber powder.
Comparative example 2
The antibacterial foam pad of this comparative example was basically the same as that of example 1 in the raw material composition and the preparation procedure, except that the antibacterial liquid-impregnated treatment of step S2 was not performed in the preparation procedure of the antibacterial foam pad of this comparative example.
Comparative example 3
The antibacterial foam pad of this comparative example was basically the same as in example 1 in the raw material composition and the preparation procedure except that the raw material of the surface functional layer of the antibacterial foam pad of this comparative example did not contain a composite antibacterial agent.
Comparative example 4
The antibacterial foaming pad of this comparative example was basically the same as in example 1 in the raw material composition and the preparation procedure except that the raw material of the surface functional layer of the antibacterial foaming pad of this comparative example did not contain dodecafluoroheptyl propyl cage type silsesquioxane.
The antibacterial type foaming mats prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to performance test, and the performance results thereof are shown in table 1:
TABLE 1
Wherein, tensile strength and elongation are tested by a CTM6000 universal tester (Shanghai Xueqiang instrument); oxygen index was tested according to GB/T2406.2-2009.
In the rebound resilience test method, a sample of a foamed mat having a cutting length of 10 x 2cm thick is placed on a plate having a flat surface, a steel ball having a weight of 50g is dropped from a height of 1m from the sample so that the ball collides with the sample, and the rebound resilience of the sample is obtained by measuring the rebound resilience after the sample is impacted.
The antibacterial property test method is carried out according to the national standard GB15979-1995 'method for testing antibacterial and sterilizing Properties and stability of products'.
The long-term antibacterial property test method comprises the steps of firstly, carrying out a high-pressure steam accelerated aging test on the antibacterial foaming cushion samples prepared in the examples 1-3 and the comparative examples 1-4 under the severe condition of 80 ℃ and saturated steam pressure of 14psi, and testing for 72 hours; taking out the product and carrying out antibacterial property test according to the national standard GB15979-1995 method for testing antibacterial and sterilizing properties and stability of the product.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims.
Claims (6)
1. An antibacterial foaming cushion is characterized by comprising a basal layer and a surface functional layer compounded on the basal layer; the surface functional layer is composed of the following raw materials in parts by weight: 80 to 100 parts of PVC paste resin, 20 to 30 parts of acrylate resin, 1 to 3 parts of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 3 to 8 parts of plasticizer, 5 to 15 parts of composite antibacterial agent, 1.5 to 2.5 parts of pigment, 2 to 5 parts of sodium dodecyl polyoxyethylene ether sulfate, 0.5 to 3.5 parts of heat stabilizer and 15 to 30 parts of solvent; the composite antibacterial agent is nano metal particles coated by pyridinium derivatives; the substrate layer is prepared from raw materials compounded by PVC powder, modified waste rubber powder, a plasticizer, a foaming agent, inorganic filler, antibacterial liquid, a heat stabilizer and a solvent; the antibacterial liquid is prepared by compounding pyridinium ionic liquid shown in a structural formula I and tetrahydrofuran,
，
wherein, the ratio of m to n is 2:3;
the modification method of the modified waste rubber powder comprises the following steps: 100 parts of waste rubber powder and 10-30 parts of PVC powder are weighed according to parts by weight and added into an internal mixer, then methacrylic acid ester which is 5-10% of the mass of the waste rubber powder and an initiator which is 0.1-0.5% of the mass of the waste rubber powder are added, and after swelling and mixing uniformly, the modified waste rubber powder is obtained through vulcanization and interface reaction at the vulcanization temperature of 100-200 ℃.
2. The antimicrobial foam mat of claim 1 wherein said acrylate resin is at least one of ethyl acrylate, butyl acrylate, methacrylate, n-butyl methacrylate, methyl methacrylate, and hydroxyethyl methacrylate.
3. The antimicrobial foam mat of claim 1 wherein the plasticizer is at least one of dioctyl phthalate, dibutyl phthalate, dinonyl phthalate, butyl benzyl phthalate.
4. The antimicrobial foam mat of claim 1 wherein said heat stabilizer is at least one of zinc stearate, calcium stearate, di-n-butyltin dilaurate.
5. The antimicrobial foam mat of claim 1 wherein the foaming agent is compounded from azodicarbonamide or N, N-dinitroso pentamethylene tetramine with sodium bicarbonate.
6. A method of preparing an antimicrobial foamed mat according to any one of claims 1 to 5, comprising the steps of:
step S1: foaming and molding a substrate layer raw material compounded by 50-100 parts of PVC powder, 8-16 parts of modified waste rubber powder, 12-20 parts of plasticizer, 2-6 parts of foaming agent, 2-6 parts of inorganic filler, 0.5-3.5 parts of heat stabilizer and 15-30 parts of solvent in a mold to obtain a substrate layer;
step S2: preparing an antibacterial solution by combining pyridinium ionic liquid and tetrahydrofuran, and soaking the substrate layer obtained in the step S1 in the antibacterial solution for 10-60 min;
step S3: mixing 80-100 parts of PVC paste resin, 20-30 parts of acrylate resin, 1-3 parts of dodecafluoroheptyl propyl polyhedral oligomeric silsesquioxane, 3-8 parts of plasticizer, 5-15 parts of composite antibacterial agent, 1.5-2.5 parts of pigment, 2-5 parts of sodium dodecyl polyoxyethylene ether sulfate, 0.5-3.5 parts of heat stabilizer and 15-30 parts of solvent into mixed emulsion, coating the mixed emulsion on the substrate layer treated in the step S2 in a spraying manner, and curing to obtain the antibacterial foaming pad compounded with the surface functional layer.
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| CN112323507A (en) * | 2020-09-30 | 2021-02-05 | 广东远华新材料股份有限公司 | Mildew-proof antibacterial crawling pad and preparation method thereof |
| CN114196136A (en) * | 2021-12-27 | 2022-03-18 | 广东远华新材料股份有限公司 | PVC yoga mat and preparation method thereof |
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2022
- 2022-04-11 CN CN202210372309.8A patent/CN115785517B/en active Active
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|---|---|---|---|---|
| WO1998039148A1 (en) * | 1997-03-03 | 1998-09-11 | Reinhard Krieg | Method for replastifying used rubber powder |
| WO2001014464A1 (en) * | 1999-08-23 | 2001-03-01 | Liu, Guixing | Thermoplastic elastomer produced from waste rubber powder/plastic and the article made therefrom |
| WO2017067504A1 (en) * | 2015-10-21 | 2017-04-27 | 大电塑料（上海）有限公司 | Foamed pvc material, preparation method and use thereof |
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| CN114196136A (en) * | 2021-12-27 | 2022-03-18 | 广东远华新材料股份有限公司 | PVC yoga mat and preparation method thereof |
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| CN115785517A (en) | 2023-03-14 |
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