CN110564076A - NBR/PVC composite floor mat and preparation method thereof - Google Patents
NBR/PVC composite floor mat and preparation method thereof Download PDFInfo
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- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
the invention provides an NBR/PVC composite floor mat, which consists of 100 parts of polyvinyl chloride resin, 10-16 parts of nitrile rubber, 9-14 parts of foaming agent, 27-40 parts of plasticizer, 2-3 parts of stabilizer, 1-2 parts of anti-aging agent, 1-4 parts of reinforcing agent, 0-2 parts of accelerator and 2-8 parts of fixing agent by mass, wherein the fixing agent is polyglycerol unsaturated fatty acid ester, and the surface of the composite floor mat is also coated with an antifouling antibacterial coating. The flexibility of the PVC foam material is improved by adding the nitrile rubber, and the migration of the plasticizer is reduced by adding the polyglycerol unsaturated fatty acid ester as the fixing agent of the plasticizer.
Description
Technical Field
The invention relates to the field of PVC (polyvinyl chloride) foaming materials, in particular to an NBR (nitrile-butadiene rubber)/PVC (polyvinyl chloride) composite ground mat and a preparation method thereof.
background
PVC is a common thermoplastic high polymer plastic, a linear high polymer is polymerized from vinyl chloride monomer under the action of a proper initiator, the linear high polymer has stable performance at normal temperature, higher mechanical strength, good chemical corrosion resistance and insulating performance, different additives can be added in the processing process to improve the relevant performance, but the impact resistance, tear resistance, flexibility, heat resistance and light stability are not high, and in order to improve the processability and the flexibility, a large amount of plasticizer is required to be added, the plasticizer is colorless and tasteless or has slight aromatic flavor, is insoluble in water, is soluble in an organic solvent, is in a free state in the plastic, can migrate to the environment, not only causes the reduction of mechanical properties, but also influences the health of human bodies.
due to the excellent comprehensive performance of the PVC material, the PVC material is widely applied to the field of ground mats, and the ground mats have severe service environment conditions, are easy to breed bacteria, are easy to adhere and dirty, are not easy to clean and influence the service life.
disclosure of Invention
Aiming at the problems, the invention provides an NBR/PVC composite ground mat and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
an NBR/PVC composite ground mat is composed of 100 parts of polyvinyl chloride resin, 10-16 parts of nitrile rubber, 9-14 parts of foaming agent, 27-40 parts of plasticizer, 2-3 parts of stabilizer, 1-2 parts of anti-aging agent, 1-4 parts of reinforcing agent, 0-2 parts of accelerator and 2-8 parts of fixing agent by mass, wherein the fixing agent is polyglycerol unsaturated fatty acid ester, and the surface of the composite ground mat is also coated with an antifouling antibacterial coating;
preferably, the polyglycerol unsaturated fatty acid ester is generated by the reaction of polyglycerol with the average polymerization degree of 2-5 and unsaturated fatty acid, and the esterification rate is 50-60%;
further preferably, the unsaturated fatty acid is oleic acid;
Preferably, the plasticizer is DOP;
Preferably, the antifouling and antibacterial coating is a random copolymer of 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate and 4-allyl catechol;
Further preferably, the antifouling and antibacterial coating is a random copolymer of 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate and 4-allyl catechol in a molar ratio of 5:2: 3;
Preferably, the foaming agent is an AC foaming agent, and the accelerator is vulcanized dithiocarbamate;
Preferably, the stabilizer is a calcium-zinc composite stabilizer or a barium-zinc composite stabilizer, and the anti-aging agent is antioxidant MBZ or antioxidant 4010NA or antioxidant RD;
Preferably, the reinforcing agent is calcium carbonate whiskers with a surface modified by sodium stearate.
the invention has the beneficial effects that:
(1) The nitrile rubber and the polyvinyl chloride have similar polarity and better compatibility, and the nitrile rubber and the polyvinyl chloride are blended and modified, so that the composite material has the elasticity and toughness of the nitrile rubber and the plasticity and chemical corrosion resistance of the polyvinyl chloride.
(2) the polyglycerol unsaturated fatty acid ester is used as a fixing agent, so that the interaction between the PVC matrix and the plasticizer molecules is enhanced, the migration of the plasticizer is reduced, and the polyglycerol unsaturated fatty acid ester also has a certain plasticizing effect on the PVC matrix.
(3) the antifouling and antibacterial coating improves the surface hydrophilicity and the biological pollution resistance of the floor mat, and the quaternary ammonium cation endows the floor mat with excellent antibacterial performance, so that the application range and the service life of the floor mat are improved.
Detailed Description
the invention is further described with reference to the following examples.
The embodiment of the application relates to an NBR/PVC composite floor mat, which consists of 100 parts by mass of polyvinyl chloride resin, 10-16 parts by mass of nitrile rubber, 9-14 parts by mass of foaming agent, 27-40 parts by mass of plasticizer, 2-3 parts by mass of stabilizer, 1-2 parts by mass of anti-aging agent, 1-4 parts by mass of reinforcing agent, 0-2 parts by mass of accelerator and 2-8 parts by mass of fixing agent, wherein the fixing agent is polyglycerol unsaturated fatty acid ester, and the surface of the composite floor mat is also coated with an antifouling antibacterial coating;
The plasticizer is usually added into the plastic polymer in the form of an external plasticizer, the two do not generate chemical reaction, but are mutually dissolved to form a homogeneous mixed system, the homogeneous mixed system is inserted between polymer molecular chains, the flexibility, the processability and the impact resistance are improved, the polyglycerol unsaturated fatty acid ester is used as the fixing agent, the fixing effect of PVC and the plasticizer is enhanced by the two-section structure of the polyglycerol unsaturated fatty acid ester, and the migration and precipitation of the plasticizer are reduced;
preferably, the polyglycerol unsaturated fatty acid ester is generated by the reaction of polyglycerol with the average polymerization degree of 2-5 and unsaturated fatty acid, and the esterification rate is 50-60%;
further preferably, the unsaturated fatty acid is oleic acid;
preferably, the plasticizer is DOP;
Preferably, the antifouling and antibacterial coating is a random copolymer of 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate and 4-allyl catechol;
Further preferably, the antifouling and antibacterial coating is a random copolymer of 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate and 4-allyl catechol in a molar ratio of 5:2: 3;
2-methacryloyloxyethyl phosphorylcholine (2-methacryloyloxyethyl phosphorylcholine) copolymer is coated on the surface of a material, which is an important way for simply and effectively improving the hydrophilicity and the biological pollution resistance of the surface of the material, but the problem of low adhesion strength exists, on the basis of the copolymer, quaternized dimethylaminoethyl methacrylate and 4-allyl catechol are added for copolymerization, wherein quaternary ammonium cationic groups provide excellent antibacterial performance for a composite ground mat, and the catechol structure is easy to adhere to the polar PVC surface, so that the adhesion strength of the coating is improved, and the surface hydrophilicity and the biological pollution resistance are improved;
Preferably, the foaming agent is an AC foaming agent, and the accelerator is vulcanized dithiocarbamate;
Preferably, the stabilizer is a calcium-zinc composite stabilizer or a barium-zinc composite stabilizer, and the anti-aging agent is antioxidant MBZ or antioxidant 4010NA or antioxidant RD;
Preferably, the reinforcing agent is calcium carbonate whisker with modified surface of sodium stearate;
the calcium carbonate crystal whisker has a perfect internal structure and a high length-diameter ratio, has high strength, and has extremely superior elongation and elastic modulus, can be compatible with a matrix to show a remarkable reinforcing and toughening effect, but can easily agglomerate in the polymer matrix due to high surface energy.
The embodiment of the application also relates to a preparation method of the NBR/PVC composite ground mat, which comprises the following steps:
s1, mixing glycerol and 3-5 wt.% of sodium hydroxide, gradually heating to 240-250 ℃ under the protection of nitrogen, refluxing for 2-6h while stirring, allowing polymerization reaction to occur, monitoring the average polymerization degree of a product in the reaction process, stopping the reaction when the average polymerization degree reaches 2-5, self-cooling, adding unsaturated fatty acid 2-4 times the mass of a system, gradually heating to 170-200 ℃ under the protection of nitrogen while stirring, allowing the product to react, monitoring the esterification rate of the product in the reaction process, stopping the reaction when the esterification rate reaches 50-60%, evaporating redundant unsaturated fatty acid under reduced pressure, and extracting with chloroform to obtain polyglycerol unsaturated fatty acid ester;
s2, weighing 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate and 4-allylcatechol according to a molar ratio of 5:2:3, dissolving the 2-methacryloyloxyethyl phosphorylcholine, the quaternized dimethylaminoethyl methacrylate and the 4-allylcatechol in absolute ethanol, dissolving azodiisobutyronitrile accounting for 1% of the mass of the monomer in absolute tetrahydrofuran, and adding half of the solution into the monomer mixed solution; heating 10mL of absolute ethyl alcohol to 70 ℃ under the protection of nitrogen, adding the rest of initiator solution, slowly dropwise adding monomer solution, continuously reacting for 24 hours after dropwise adding is finished for 3-4 hours, stopping reaction, concentrating to 15-20mL, dialyzing by a dialysis bag, carrying out freeze drying after dialysis is finished, obtaining a terpolymer, and preparing a 2mg/mL solution by using the absolute ethyl alcohol for later use;
S3, preparing 10% calcium carbonate whisker-water suspension by mass, stirring and dispersing, heating to 60-70 ℃, dropwise adding 50% of 8% sodium stearate-ethanol solution by mass of the system, keeping the temperature, stirring and reacting for 4 hours, filtering out precipitates, respectively washing acetone and water, and drying in vacuum to obtain the sodium stearate surface modified calcium carbonate whisker;
s4, plasticating polyvinyl chloride, a plasticizer and a stabilizer through an open mill, adding nitrile rubber for mixing, sequentially adding a foaming agent, an anti-aging agent, a reinforcing agent, an accelerator and polyglycerol unsaturated fatty acid ester to prepare paste, pouring the prepared paste into a mold, putting the mold into a heater, closing the mold, carrying out mold pressing for 20min under the conditions of heating and pressurizing, cooling, then removing the pressure of a hot press, demolding to obtain a semi-foaming mold pressing block with certain elasticity, putting the obtained mold pressing block into a 110 ℃ oven for 2h treatment, cooling the oven to normal temperature, and then spraying an antifouling antibacterial coating on the surface to obtain the composite floor mat material.
Example 1
an NBR/PVC composite ground mat is composed of 100 parts of polyvinyl chloride resin, 10 parts of nitrile rubber, 10 parts of foaming agent, 30 parts of plasticizer, 2 parts of stabilizer, 1 part of anti-aging agent, 2 parts of reinforcing agent, 1 part of accelerator and 2 parts of fixing agent by mass, wherein the fixing agent is polyglycerol unsaturated fatty acid ester, and the surface of the composite ground mat is also coated with an antifouling antibacterial coating; the preparation method of the NBR/PVC composite ground mat comprises the following steps:
s1, mixing glycerol and 3-5 wt.% of sodium hydroxide, gradually heating to 240-250 ℃ under the protection of nitrogen, refluxing for 2-6h while stirring, allowing polymerization reaction to occur, monitoring the average polymerization degree of a product in the reaction process, stopping the reaction when the average polymerization degree reaches 2-5, self-cooling, adding unsaturated fatty acid 2-4 times the mass of a system, gradually heating to 170-200 ℃ under the protection of nitrogen while stirring, allowing the product to react, monitoring the esterification rate of the product in the reaction process, stopping the reaction when the esterification rate reaches 50-60%, evaporating redundant unsaturated fatty acid under reduced pressure, and extracting with chloroform to obtain polyglycerol unsaturated fatty acid ester;
s2, weighing 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate and 4-allylcatechol according to a molar ratio of 5:2:3, dissolving the 2-methacryloyloxyethyl phosphorylcholine, the quaternized dimethylaminoethyl methacrylate and the 4-allylcatechol in absolute ethanol, dissolving azodiisobutyronitrile accounting for 1% of the mass of the monomer in absolute tetrahydrofuran, and adding half of the solution into the monomer mixed solution; heating 10mL of absolute ethyl alcohol to 70 ℃ under the protection of nitrogen, adding the rest of initiator solution, slowly dropwise adding monomer solution, continuously reacting for 24 hours after dropwise adding is finished for 3-4 hours, stopping reaction, concentrating to 15-20mL, dialyzing by a dialysis bag, carrying out freeze drying after dialysis is finished, obtaining a terpolymer, and preparing a 2mg/mL solution by using the absolute ethyl alcohol for later use;
S3, preparing 10% calcium carbonate whisker-water suspension by mass, stirring and dispersing, heating to 60-70 ℃, dropwise adding 50% of 8% sodium stearate-ethanol solution by mass of the system, keeping the temperature, stirring and reacting for 4 hours, filtering out precipitates, respectively washing acetone and water, and drying in vacuum to obtain the sodium stearate surface modified calcium carbonate whisker;
s4, plasticating polyvinyl chloride, a plasticizer and a stabilizer through an open mill, adding nitrile rubber for mixing, sequentially adding a foaming agent, an anti-aging agent, a reinforcing agent, an accelerator and polyglycerol unsaturated fatty acid ester to prepare paste, pouring the prepared paste into a mold, putting the mold into a heater, closing the mold, carrying out mold pressing for 20min under the conditions of heating and pressurizing, cooling, then removing the pressure of a hot press, demolding to obtain a semi-foaming mold pressing block with certain elasticity, putting the obtained mold pressing block into a 110 ℃ oven for 2h treatment, cooling the oven to normal temperature, and then spraying an antifouling antibacterial coating on the surface to obtain the composite floor mat material.
example 2
an NBR/PVC composite ground mat is composed of 100 parts of polyvinyl chloride resin, 15 parts of nitrile rubber, 14 parts of foaming agent, 40 parts of plasticizer, 3 parts of stabilizer, 2 parts of anti-aging agent, 3 parts of reinforcing agent, 2 parts of accelerator and 8 parts of fixing agent by mass, wherein the fixing agent is polyglycerol unsaturated fatty acid ester, and the surface of the composite ground mat is also coated with an antifouling antibacterial coating; the preparation method of the NBR/PVC composite ground mat comprises the following steps:
s1, mixing glycerol and 3-5 wt.% of sodium hydroxide, gradually heating to 240-250 ℃ under the protection of nitrogen, refluxing for 2-6h while stirring, allowing polymerization reaction to occur, monitoring the average polymerization degree of a product in the reaction process, stopping the reaction when the average polymerization degree reaches 2-5, self-cooling, adding unsaturated fatty acid 2-4 times the mass of a system, gradually heating to 170-200 ℃ under the protection of nitrogen while stirring, allowing the product to react, monitoring the esterification rate of the product in the reaction process, stopping the reaction when the esterification rate reaches 50-60%, evaporating redundant unsaturated fatty acid under reduced pressure, and extracting with chloroform to obtain polyglycerol unsaturated fatty acid ester;
S2, weighing 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate and 4-allylcatechol according to a molar ratio of 5:2:3, dissolving the 2-methacryloyloxyethyl phosphorylcholine, the quaternized dimethylaminoethyl methacrylate and the 4-allylcatechol in absolute ethanol, dissolving azodiisobutyronitrile accounting for 1% of the mass of the monomer in absolute tetrahydrofuran, and adding half of the solution into the monomer mixed solution; heating 10mL of absolute ethyl alcohol to 70 ℃ under the protection of nitrogen, adding the rest of initiator solution, slowly dropwise adding monomer solution, continuously reacting for 24 hours after dropwise adding is finished for 3-4 hours, stopping reaction, concentrating to 15-20mL, dialyzing by a dialysis bag, carrying out freeze drying after dialysis is finished, obtaining a terpolymer, and preparing a 2mg/mL solution by using the absolute ethyl alcohol for later use;
s3, preparing 10% calcium carbonate whisker-water suspension by mass, stirring and dispersing, heating to 60-70 ℃, dropwise adding 50% of 8% sodium stearate-ethanol solution by mass of the system, keeping the temperature, stirring and reacting for 4 hours, filtering out precipitates, respectively washing acetone and water, and drying in vacuum to obtain the sodium stearate surface modified calcium carbonate whisker;
S4, plasticating polyvinyl chloride, a plasticizer and a stabilizer through an open mill, adding nitrile rubber for mixing, sequentially adding a foaming agent, an anti-aging agent, a reinforcing agent, an accelerator and polyglycerol unsaturated fatty acid ester to prepare paste, pouring the prepared paste into a mold, putting the mold into a heater, closing the mold, carrying out mold pressing for 20min under the conditions of heating and pressurizing, cooling, then removing the pressure of a hot press, demolding to obtain a semi-foaming mold pressing block with certain elasticity, putting the obtained mold pressing block into a 110 ℃ oven for 2h treatment, cooling the oven to normal temperature, and then spraying an antifouling antibacterial coating on the surface to obtain the composite floor mat material.
Comparative example
as in example 1, no fixing agent of polyglycerin unsaturated fatty acid ester was added.
Detection experiment:
1. Surface migration test
Wiping the surface (without a coating) of the composite ground mat by using a cotton ball with cyclohexane, drying the composite ground mat in an oven at a low temperature (50 ℃) for 2 hours to volatilize a surface solvent, weighing the mass by using an analytical balance, and calculating the migration rate; and (3) placing the composite ground mat (without the coating) in an environment of 38 ℃ and-10 ℃ for 480h, taking out, wiping the surface by using a cotton ball with cyclohexane, drying the surface in an oven for 2h to evaporate a surface solvent, weighing the mass by using an analytical balance, and calculating the migration rate. The results of the measurements are shown in the following table.
| The migration rate/%) | Example 1 | example 2 | Comparative example |
| untreated | 0.12 | 0.07 | 0.75 |
| High temperature treatment (38 ℃ C.) | 0.12 | 0.08 | 0.84 |
| low temperature treatment (-10 ℃ C.) | 0.15 | 0.11 | 1.16 |
2. Coating stability test
The ground mat samples were immersed in the aqueous solution for 12 hours, treated at 50 ℃ for 6 hours, and left at room temperature for 6 months, and the change in the surface contact angle was measured using the untreated samples as a control.
The contact angles of the samples which are soaked in water for 12 hours, treated for 6 hours in an environment of 50 ℃ and placed at room temperature for 6 months are respectively 43 degrees, 45 degrees and 45 degrees, and the comparative example is 42 degrees.
finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The NBR/PVC composite floor mat is characterized by comprising 100 parts of polyvinyl chloride resin, 10-16 parts of nitrile rubber, 9-14 parts of foaming agent, 27-40 parts of plasticizer, 2-3 parts of stabilizer, 1-2 parts of anti-aging agent, 1-4 parts of reinforcing agent, 0-2 parts of accelerator and 2-8 parts of fixing agent by mass, wherein the fixing agent is polyglycerol unsaturated fatty acid ester, and the surface of the composite floor mat is further coated with an antifouling antibacterial coating.
2. the NBR/PVC composite floor mat as in claim 1, wherein the polyglyceryl unsaturated fatty acid ester is formed by reacting polyglyceryl having an average degree of polymerization of 2 to 5 with unsaturated fatty acid, and the esterification rate is 50 to 60%.
3. The NBR/PVC composite floor mat according to claim 1, wherein the unsaturated fatty acid is oleic acid.
4. The NBR/PVC composite floor mat according to claim 1, wherein the plasticizer is DOP.
5. the NBR/PVC composite floor mat of claim 1, wherein the anti-fouling and anti-microbial coating is a random copolymer of 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate, 4-allylcatechol.
6. The NBR/PVC composite floor mat of claim 1, wherein the anti-fouling and anti-bacterial coating is a random copolymer of 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate, 4-allylcatechol in a molar ratio of 5:2: 3.
7. The NBR/PVC composite floor mat according to claim 1, wherein the foaming agent is an AC foaming agent and the accelerator is a vulcanized dithiocarbamate.
8. the NBR/PVC composite floor mat according to claim 1, characterized in that the stabilizer is calcium zinc composite stabilizer or barium zinc composite stabilizer, and the anti-aging agent is anti-aging agent MBZ or anti-aging agent 4010NA or anti-aging agent RD.
9. The NBR/PVC composite floor mat according to claim 1, wherein the reinforcing agent is calcium carbonate whiskers surface-modified with sodium stearate.
10. A preparation method of NBR/PVC composite ground mat is characterized by comprising the following steps:
S1, mixing glycerol and 3-5 wt.% of sodium hydroxide, gradually heating to 240-250 ℃ under the protection of nitrogen, refluxing for 2-6h while stirring, allowing polymerization reaction to occur, monitoring the average polymerization degree of a product in the reaction process, stopping the reaction when the average polymerization degree reaches 2-5, self-cooling, adding unsaturated fatty acid 2-4 times the mass of a system, gradually heating to 170-200 ℃ under the protection of nitrogen while stirring, allowing the product to react, monitoring the esterification rate of the product in the reaction process, stopping the reaction when the esterification rate reaches 50-60%, evaporating redundant unsaturated fatty acid under reduced pressure, and extracting with chloroform to obtain polyglycerol unsaturated fatty acid ester;
S2, weighing 2-methacryloyloxyethyl phosphorylcholine, quaternized dimethylaminoethyl methacrylate and 4-allylcatechol according to a molar ratio of 5:2:3, dissolving the 2-methacryloyloxyethyl phosphorylcholine, the quaternized dimethylaminoethyl methacrylate and the 4-allylcatechol in absolute ethanol, dissolving azodiisobutyronitrile accounting for 1% of the mass of the monomer in absolute tetrahydrofuran, and adding half of the solution into the monomer mixed solution; heating 10mL of absolute ethyl alcohol to 70 ℃ under the protection of nitrogen, adding the rest of initiator solution, slowly dropwise adding monomer solution, continuously reacting for 24 hours after dropwise adding is finished for 3-4 hours, stopping reaction, concentrating to 15-20mL, dialyzing by a dialysis bag, carrying out freeze drying after dialysis is finished, obtaining a terpolymer, and preparing a 2mg/mL solution by using the absolute ethyl alcohol for later use;
s3, preparing 10% calcium carbonate whisker-water suspension by mass, stirring and dispersing, heating to 60-70 ℃, dropwise adding 50% of 8% sodium stearate-ethanol solution by mass of the system, keeping the temperature, stirring and reacting for 4 hours, filtering out precipitates, respectively washing acetone and water, and drying in vacuum to obtain the sodium stearate surface modified calcium carbonate whisker;
s4, plasticating polyvinyl chloride, a plasticizer and a stabilizer through an open mill, adding nitrile rubber for mixing, sequentially adding a foaming agent, an anti-aging agent, a reinforcing agent, an accelerator and polyglycerol unsaturated fatty acid ester to prepare paste, pouring the prepared paste into a mold, putting the mold into a heater, closing the mold, carrying out mold pressing for 20min under the conditions of heating and pressurizing, cooling, then removing the pressure of a hot press, demolding to obtain a semi-foaming mold pressing block with certain elasticity, putting the obtained mold pressing block into a 110 ℃ oven for 2h treatment, cooling the oven to normal temperature, and then spraying an antifouling antibacterial coating on the surface to obtain the composite floor mat material.
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Application publication date: 20191213 |